AN ODYSSEY TO NANOGEOSCIENCE

Thrivikramji.K.P.
thrivikramji@gmail.com

INTRODUCTION

Nanoscience is the science of ultra small objects or particles in the nanodomain (i.e. at least one
dimension < 100 nm and one nm is one millionth of a mm or 10E-9 m or 10 Angstroms), which have
characteristically a large surface area to volume ratio. For example, the diameter of human hair is only
80,000 nm. At such ultra small sizes, the physical size and shape influence and dictate the variations of
thermodynamic, mechanical, electrical and structural, optical and/or chemical property variations. Thereby
the nanoscience becomes unique and important to geoscience and especially in nanogeochemistry,
which plays out in an outstanding manner in the processes of the critical zone of the earth system Jordan,
2001). The Lycurgus Cup, now in British Museum, is a 4th Century Roman artifact (appearing greenish in
reflected light but reddish in transmitted light) is the first ever object that made use of nanoscience in its
making as revealed by later studies.

In a NRC book entitled Basic Research Opportunities in Earth Science , Jordan (2001), defined the
critical zone as the realm, where land meets the fluid envelopes of the Earth, i.e., hydrosphere &
atmosphere. Fresh water, agriculture, many vital natural resources such as most mineral deposits &
timber are native to this zone. The utmost heterogeneity of this zone is a direct outcome of a combination
of the Geo & bio attributes. Based on Physical, geochemical, and biologic processes, four principal &
overarching categories have been identified (Table.1).

In fact the nanogeochemical processes dominate the critical zone. Processes of elemental distribution,
Biologic abiotic Earth interaction, heterogeneous catalysis reaction pathways and mineral growth,
mineral transformation and weathering are operating nanoscale phenomena in geomaterials of the
nanodomain.

Relevance to the Society

Though, a relatively emerging field of science, nanoscience and technology have found of tremendous
potential applications in several fields like environmental safety, National security and Human health;
Mining, minerals, oil and gas; Environment friendly manufacturing & new geoomimetic materials and
agriculture and food. For furthering or fostering growth in this field, special technologies, samples and
better co-ordination among the various research institutions are a necessity. Creation of distributed
research centers, education focused on manpower creation and training along with improved
communication with public are also recommended.

The Feynman-Smalley-Drexler Trio & Beginnings of Nanotechnology

In 1959, Richard P. Feynman, a physicist, who participated in the WW2 Manhattan Project in Los
Alamos, declared that there is plenty of room at the bottom implying that scaling down to nano level and
starting from the bottom was the key to future progress in science and technology. Richard Smalley, a
professor at Rice University and a 1996 Nobel in Chemistry along with Robert Curl & Harold Kroto for
discovery of the buckminsterfullerene form of carbon, laid the foundation of carbon-nanotube research.
Despite all the adverse criticisms, Eric Drexler (co-founder of the Foresight Institute, Ta.) developed the
idea of using nanotechnology in building molecular assemblers that would manufacture materials with
atomic precision and his writings have certainly raised public excitement with the idea of nanotechnology-

NANOGEOSCIENCE
In Geoscience, chemical behavior of any material is the sum of reaction affinities and kinetics to
bioavailability, while Nanogeoscience addresses the geologic processes on our & other planets involving
materials and processes at nanoscale and in the nanodomain. Nevertheless, it is more complex and at

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the same time much more realistic. In the nanodomain, boundary between chemistry, physics & materials
science is more diffuse.

Atmosphere, yet another focal theme of Nanogeoscience, has the nanoparticles and aerosols in the air
column which are central to the properties & chemical dynamics of the atmosphere. Further, the
nanoparticles are a major influencer of workings of our oceans and solid planet. In minerals studied to
date in the nanorange, these variations are most pronounced below a few 10s of nm and can be dramatic
under 10 nm. Geoscientists study quantitatively the mineral nanoparticle properties and compare them
with the properties of macro-grains of same mineral.

Taxonomy in Nanodomain
Hochella, Jr. (2008) classified nano-geo-materials into two broad categories, viz., nanominerals and
mineral nanoparticles (Table 2). Despite their uncharted distribution, oceans may still hold the largest
complement of nanodomain materials with the major inputs from the atmosphere, river and glacial melt-
water discharge and aerosol deposition.

Reaction Kinetics
For example, Iron, a common transition metal in some domains of critical zone, occurs in multi-valence
states in the minerals as well as in the geochemical environment. But in the latter it manifests in one or
more forms as hydrated ion, metal complexed in a small protein, metal adsorbed in surface of 1.0nm
mineral nanoparticles, as metal adsorbed to the same mineral except 20 nm in size and metal adsorbed
to same mineral of 200 nm in size.

In the nanodomain, metals, in each of the five states, show significantly (potentially & dramatically)
different chemical behaviors, which is the sum of reaction affinities & kinetics to bioavailability. Though,
chemically, hydrated ion of a transition metal is a single dissolved species, in Geoscience, particles <0.22
m are treated as dissolved substances

Nanoparticles of 2 - 20 nm range carry a good deal of element iron, which reaches the ocean as
dissolved organic and inorganic complexes. While the productivity of oceans depends on availability or
supply of nutrients in the first place, oceanic Iron flux via Fe-containing nanoparticles, far exceeds riverine
input. As oceanic phytoplanktons perform nearly 50% photosynthesis, then these micros are as effective
as the terrestrial plants, as they play a crucial role in balancing excess CO2. . .

Value of Nanogeoscience
The most important threats faced by humanity in this century is perhaps not HIV-AIDS, famine or
population explosion but climate change. With continued Antarctic ice melting, iron in mineral
nanoparticles is bioavailable to various species of marine phytoplankton making them more important
source of Oceanic iron.

Near surface terrestrial environment is now notorious for toxic metal transport by way of soils, ground
water and as aerosols. For example, researchers have concluded that radio nuclides are transported by
groundwater through several tens of kilometers but over short periods of time and defying the
thermodynamics based predictions. A compelling example can be noticed in a nuclear waste processing
plant near Mayak, Russia. Here transport of 70 to 90% of the plutonium in groundwater is by way of ferric
oxides <15 nm, as well as via a few other nanophases- a kind of piggy back ride..

A research supported by US Superfund to clean up the rivers and rivers basins in the US was
implemented in a contaminated area (=1600 km2) - the largest Superfund site- in western Montana,USA
(Hochella Jr, 2008). The chief contaminants like, Cu, Zn, As, Pb, and Cd, originated from a mine waste
due to a century and half of mining. Metals moved many hundreds of kilometers down the hydrologic
gradient & across floodplains in the Clark Fork River basin. The carriers were none other than
nanominerals and mineral nanoparticles of manganese and iron oxyhydroxides (Hochella Jr. et al. 2005).

In the study of potential earthquake sites, nanotechnology has its own new roles, how ever small they be.
As it stands to day the mechanical properties of particles in the Nanodomain are much less understood,

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and hence their impact on the earth s working. Consequently, this is a rewarding research area still
remains to be tapped. Mineral nanoparticles are produced naturally by mechanical grinding associated
with earthquake-generating faults in shallow crust & Earth s surface. Reports on large volumes of
nanoscale mineral particles of 10 20 nm in size noticed in pulverized rock in fault zones as wide as 100
m, indicate the significance of mineral nanoparticles in fault mechanics.

Ringwoodite and wadsleyite, nanoparticles of high-pressure silicates, may have a key role in deep-focus
earthquakes (300 700 km depth) of 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 their movement.

Natural Amorphous Nanomaterials

The critical zones are also endowed with another category of nanoparticles which are known to be
amorphous. On the one hand there is very little or limited diffraction information on these and on other the
spectroscopic data are very hard to interpret or decipher. Though such particles show highly variable
chemistry and form, there is a growing awareness about the abundance and importance.

Weathering and Amorphous nanofilms

Mineral weathering had all along been an attractive topic of study by geochemists. Classical view was
that during weathering the weathered product, remains as a coating on the grain there by shutting off the
un-weathered portions from the attack by the solvent solutions. However, the advent of SEM and electron
probe tools opened a new vista on the weathering process and dispensation of the weathering products.
The concept of the protective coating on the grains during advanced stage weathering became untenable
and obsolete and the mineral cracks and cleavages became the conduits of transport and flow of
weathering fluids.

But studies of the Nanodomain particles provided a new perception to the process of weathering or
neomineral formation. 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. It was also inferred that the scale of weathering was much slower
in t he natural conditions than in the laboratory reactor. Weathering rate of K-feldspars is 10E5 times
slower under natural conditions than under similar multiyear-long weathering experiments.

Amorphous nanofilms on uranium-containing pyrochlore (a calcium titanate considered for immobilizing

fissile elements), slows release of U (Stubbs et al. 2008). And hence may have a crucial role in dictating
uranium s mobility through the vadose zone. Though the Clark Fork riverbed and Floodplains, Mo has
reducing zones of river bed with amorphous, aggregated Zn-sulfide nanoparticles, their environmental
role still remains almost nearly unknown (a rewarding research opportunity) and such amorphous, metal-
bearing, naturally occurring nanomaterials are still undocumented or unprofiled. Recent studies showed
secondary amorphous silica with toxic heavy metals are relatively common.

Nanomaterials are not only earth centric, but they are also known to occur in interplanetary and
interstellar space and solar system. Interpretation of data gathered by spectral imagers (Mars Viking and
Pathfinder landers) and ground based observations strongly indicate presence of nanophase ferric
oxides in the Martian soils and atmosphere (Bell et al. 2000; Morris et al. 2000). In addition, diamond
nanoparticles averaging 2 to 3 nm diameter and grains as small as 1 nm (<150 carbon atoms) in minute
quantities have been separated by a multistep acid digestion of (like burning down the haystack to find
the needle ) Chondritic meteorites & Interplanetary Dust Particles

What about the Immediate Future?

The next big question is whether Nanogeo or nanobio products or processes are going to be the next big
thing or is it really nanopores or mesopores. The inorganic nano-systems would include the living things
or organisms, which symbolize a vast array of structures and mechanisms. The Nanobiomachines a.k.a.,
molecular motors are built on principles governed by nanoscale physics & chemistry. Better perception of

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behaviour and characteristics of natural nanoscale biological properties are essential to better appreciate
inorganic systems and nanogeo and nanobio interactions.

Nanopores (<2 nm of free diameter a.k.a. micropores), & mesopores (2 50 nm pore dia.) account for a
very large proportion of total surface area available in rocks, soils & water borne aggregates. Highly
confined pores and tubes greatly modify mineral fluid interface reaction pathways and kinetics compared
to reactions at unconfined mineral fluid interfaces. Such systems viz, nanopores and nanotubes, greatly
influence sorption, desorption and diffusion deeply affecting affecting precipitation, weathering & transport
phenomena. (e.g. Hochella and Banfield 1995; Wang et al. 2003). Gilbert et al. (2007) suggested that
surface charge, cluster growth characteristics, stability and principles of fluid dynamics dictate
aggregation/dis-aggregation behavior of natural nanoparticles in air & water. A combination of
experiments & modeling will help researchers to infer the characteristics & behavior of the nano-
aggregates.

To quote Hochella Jr, (2007) 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 .

Products and processes of nanoscience or nanotechnologies are fast becoming the next big thing (sans
the bigness)., and covers a range of disciplines & techniques rather than one spanning the whole
spectrum of science - touching medicine, physics, engineering and chemistry.

Impact on Geoscience
Undoubtedly, nanoscience definitely has profound implications in neomineral formation processes both in
sedimentary and metamorphic environments. Origin of mineral deposits of hydrothermal and metasomatic
processes are no exceptions, as the transport of components of ore minerals, their nucleation and
deposition greatly depend on nanodomain processes and kinetics. In what follows, some examples
aggregated and cited by Hochella Jr. (2002) in respect of impact of nanoscience on geosciences, are
briefly outlined.

Minerals and nanominerals in the lower troposphere do influence the radiative forcing effects and
consequently affect the global heating/cooling.. Equally importantly, formation, growth and nature of
airborne nanoparticles do have profound implications for human health as well as chemistry of
atmosphere, including heterogeneous catalysis of nanoaerosols.

The relatively high electrical conductivity of many rocks of deep crustal and mantle origin are attributed to
carbonaceous nanofilms. In contrast, organic nanofilms in volcanic rocks account for complex abiotic
heterogeneous catalysis & synthesis.

Mineral nucleation & growth in the nanodomain exercise influence on the initial growth of minerals. The
heterogeneous nanoprecipitation at the mineral/water interface in soils more or less imitates the transport
and distribution of toxic metals in the environment. Mineral surface reactivity, in the presence of nanofilms
of water, mirrors weathering reactions and formation of secondary mineral phases.

The complexation in an aqueous solution of components of polynuclear complexes and nanoclusters,

have direct implications and fundamental applications in the areas of aqueous geochemistry and
biogeochemistry. Metal sorption on nanominerals in acid mine drainage environments, have implications
to toxic metal transport in surface and groundwater systems.

Characteristics of naturally occurring magnetic nanoparticles, teach us their relationships to biological

systems, remediation strategies, medicine and so on. Nanomolecular attachments between minerals and
microbes, have a parallel in bacterial attachment and electron transport between living and non-living
systems.

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 Summary
Nanoscience, in spite of its beginnings soon after the WW2, did not earn the close attention of scientists
and technologists until the closing decades of the 20th century. The study of pyrite framboids of the sixties
and fluid inclusions of the seventies perhaps opened a new window in the study of submicroscopic or
ultramicroscopic inorganic particles and materials a precursor to Nanogeoscience.

The convergence of disciplines and research tools of material science, physics and chemistry laid the firm
foundation of nanoscience. Very much like the way geochemistry and geoscience benefited from the
developments in the physicalsciences, the nanoscience also made very tangible inroads into the realm of
earthsystem studies and birth of the discipline of Nanogeoscience.

Acknowledgements
I deeply appreciate the invitation to participate in the in the Brain Storming Session on Nanogeoscience,
(Aug. 20-21, 09) organized by the Dept. of Marine Science, Bharathidasan University Thiruchirapally,
Tamil Nadu. I also extend my deep appreciation to Dr.V.Radhakrishnan, the Geenral Convenor..
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Rreferences &Extended reading list

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Ban¢eld, J.,F, H. Zhang, (2001) Nanoparticles in the environment, Rev. Mineral. Geochem. 44, 1-58.

Bell JF and 23 coauthors (2000) Mineralogic and compositional properties of Martian soil and dust:
Results from Mars Pathfinder. Journal of Geophysical Research 105: 1721-1755

Buseck, PR, (1998) Magnetic microstructure of magnetotactic bacteria by electron holography, Science
282, 1868- 1870

Buseck, P.R ,D.J. Jacob, M. Posfai, J. Li, J.R. Anderson, (2000) Minerals in the air: An environmental
perspective, Int. Geol. Rev. 42, 577-593.

Dunin-Borkowski, R.E., M.R. McCartney, R.B. Frankel,.A. Bazylinski, M. Po sfai, P.R..Rancourt, D.G.,
(2001) Magnetism of earth, planetary, and environmental nanomaterials, Rev. Mineral. Geochem. 44,
217-292.

Gilbert B, Lu G, Kim CS (2007), Stable cluster formation in aqueous suspensions of iron oxyhydroxide
nanoparticles. Journal of Colloid and Interface Science 313: 152-159

Hochella Jr.,, M.F. J. Ban¢eld, (1995) Chemical weathering of silicates in nature: A microscopic
perspective with theoretical considerations, Rev. Mineral. 31, 353-406.

Hochella Jr., M.F J.N. Moore, U. Golla, A. Putnis, (1999) A TEM study of samples from acid mine
drainage systems: Metal^mineral association with implications for transport, Geochim. Cosmochim. Acta
63, 3395-3406

Hochella Jr., M.F, (2008) Nanogeoscience: From Origins to Cutting-Edge Applications, Elements, Vol. 4,
pp. 373 378

Hochella Jr.MF, Lower, SK, Maurice,PA, Penn,RL, Sahai,N, Sparks,DL and Twining,BS, ( 2008) ,
Nanominerals, Mineral Nanoparticles, and Earth Systems; SCIENCE VOL 319, 1631-34.

Jordan T. H., ed. (2001) Basic Research Opportunities in the Earth Sciences. National Research Council
National Academy Press, Washington, D.C., 154 pp.

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Lower, S, M.F. Hochella Jr., T.J. Beveridge, (2001) Bacterial recognition of mineral surfaces: Nanoscale
interactions between Shewanella and K-FeOOH, Science 292, 1360-1363.

Mogk, D.W,E.A. Mathez, (2000) Carbonaceous ¢lms in midcrustal rocks fromthe KTB borehole,
Germany, as characterized by time-of-£ight secondary ion mass spectrometry, Geochem. Geophys.
Geosyst. paper no.2000GC000081 (available at www.agu.org).

Morris RV and 11 coauthors (2000) Mineralogy, composition, and alteration of Mars Pathfinder rocks and
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Scheidegger, A.M, D.L. Sparks, (1996) A critical assessment of sorption-desorption mechanisms at the
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Tingle, T.N., E.A. Mathez, M.F. Hochella Jr., (1991) Carbonaceous matter in peridotites and basalt
studied by XPS, SALI, and LEED, Geochim. Cosmochim. Acta 55, 1345-1352.

Tingle, T.N., M.F. Hochella Jr., (1993) Formation of reduced carbonaceous matter in basalts and
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Table 1 Processes and attributes in the Critical Zone (Jordan, 2001)

Zone Attributes
Biologic Organism s nutritional requirements, drives a significant amount of
chemical cycling within & between water, soil, rocks &atmosphere
Weathering Constantly at work, generating soil, destroying and producing new
mineral phases in the process and redistributing elements among
water, rocks, & organic materials
Fluid Transport Critical component in water resources supply and management, as
well as everything from flooding to
landform development
Near surface tectonics Shapes the land surface through faulting, subsidence, uplift and mass
movement

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Table 2, General attributes of Geo-materials in Nanodomain (Hochella Jr., 2008)
Category Nanominerals Mineral Nanoparticles
Example Ferrihydrite (Fe-oxyhydrite) In nanorange and in sizes exceeding
Common in soils; fresh & seawater nanorange (e.g., pyrite crystals in
framboids) and reaching dimensions of
bulk minerals.
Size at/or <10 nm in dia., but never > 20 nm >20 nm or more
Habit Rods, sheets & nanoparticles; one dimension in nanodomain
Attribute No bulk equivalents, many yet to be Great majority of minerals exist as
discovered mineral nanoparticles & as bulk minerals.
Occurrence 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