U21 POSTGRADUATE RESEARCH CONFERENCE PROCEEDINGS I

Water - how need drives research and research underpins solutions to world-wide problems
20th-25th July 2008, University of Birmingham, Birmingham UK

The Influence of Synthesised Iron Oxide Nanoparticles to the Aquatic

Environment; pH and NOM Effects

Susan Cumberland and Jamie R Lead,

School of Geography, Earth & Environmental Sciences, University of Birmingham, Birmingham, UK

Background

In the past 20 years, there has been a marked increase in the applications of nanotechnology to many
industrial processes and products. Extremely small, nanoparticles, consisting of pure carbon, metal or
metal oxides with or without additional surface coatings, are defined as havi ng one dimension measuring
less than 100 nm. They are found to have remarkable properties that are not observed in the bulk
material. At 1-5 nm, quantum effects begin to dominate affecting optical, conductive and semi-conductive
properties (Alivisatos, 1996; Owen & Depledge, 2005). These properties have helped advancements in
electronics, for example, faster computers, flat screens, LCD television, digital cameras. Some
nanoparticles have photo-catalytic properties as with titanium dioxide and zinc oxide provide high sun
protection factors in clear sun creams due to a high surface area to mass ratio. Other applications include
metallic paints and thin films (Kendall et al., 2004), self cleaning windows and solar panel technology, car
tyres, hydrogen fuel storage cells and now as anti-microbial additives in laundry products (Colvin, 2003).
This nanotechnology sector has achieved a multibillion US dollar market, and is widely expected to grow
to 1 trillion US dollars by 2015 (Aitken et al., 2006). With such a huge investment and wide uses, products
containing nanoparticles inevitably will be released into the natural environment. While there are clear
benefits from the use of this technology currently, there is little understanding of what is going to happen
to them once they are there regarding fate, behaviour and transportation.

Ecotoxicology and risk of nanoparticles

A few toxicological studies have revealed that some of these nano-sized materials are more toxic than
their bulk counter parts. Studies involvi ng human and animal cells, plants and aquatic fauna (Hund-Rinke
& Simon, 2006) have found varying degrees of toxicity ranging from irritation and aggression (Smith et al.,
2007), behavioural changes due to brain oxidative stress in fish (Oberdorster, 2004), and death. This may
be due to increased mobility through the cell membrane (Koziara et al., 2003). Some products such as
carbon fullerenes (C60) and nanotubes may even interfere with DNA as they are roughly the same
dimensions (1-2nm by 1000s nm). Moreover, many nanoparticles require, sometimes toxic, organic
chemical stabilizers for them to remain in solution, and may further increase (or decrease) toxicity
(Lewinski et al., 2008). Bio-accumulation in food chains has been little studied to date, so the risk to
humans is relatively unknown.

Pollution pathways to aquatic systems

The water industry and natural aquatic systems are at particular risk to nanoparticles. Pollution pathways
may be via domestic washings of cosmetics and washing powders into municipal waste water systems.
Alternatively, nanoparticles may reach aquatic systems from accidental industrial release such as
equipment rinsing or during transportation. Using nanoparticles for soil/ water decontamination provides
yet another route to the aquatic environment.

Iron Oxide nanoparticles – a model example of metal oxide nanoparticles

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 U21 POSTGRADUATE RESEARCH CONFERENCE PROCEEDINGS I
Water - how need drives research and research underpins solutions to world-wide problems
20th-25th July 2008, University of Birmingham, Birmingham UK

The iron oxides (FeOx) are an example of a direct application of nanoparticles to the environment. Iron
oxides nanoparticles have been shown to be extremely efficient at de-contamination of persistent organic
pollutants (POPs) and arsenic. Dissolved organic carbon (DOC) found in high concentrations in peaty
catchments can be a problem in drinking water due to release of toxic gases when mixed with household
cleaners such as bleach (Giasuddin et al., 2007). Iron oxide nanoparticles have also been effective in the
removal of these organic substances. The process works as the iron oxide nanomaterials have an affinity
for DOC such as humic and fulvic acid and flocculate the colloids which then aggregate and sediment to
the bottom under normal pH conditions. In soils and groundwater, they act as a catalyst, reducing organic
pollutants to less harmful products such as methane, hydrogen gas and carbon dioxide. A few permeable
reactive barriers containing iron and iron oxide nanoparticles have been installed in some underground
aquifers through which the contaminated water flows. Here, zerovalent iron (iron that has no charge) is
more often used due to its greater reactivity. Additionally, nanoscale zerovalent iron has been shown to
be an effective treatment where there is arsenic contamination (Giasuddin et al., 2007). An oxide layer
rapidly forms around this particle so that its surface chemistry is similar to iron oxide (Sohn et al., 2006).
Iron oxide is a more suitable material to use in the laboratory as it is more stable. A carrier agent, such as
guar gum is used to transport the nanoparticles deep underground. Once in place these barriers can
remain active for many years.
Despite the advantages that might be gained from using iron reactive barriers to remediate
ground water, oxygen depletion (Zhang, 2003) and an increase in hydrogen gas coupled with an
increase in microbial population (Gu et al., 2002) have been noted side effects. Moreover, the iron oxides
have also shown cytotoxicity (Brunner et al., 2006; Lewinski et al., 2008), raising questions whether this
release of nanoparticle slurry is environmentally ethical.

Experimental Section: Behaviour to different pH and NOM concentrations

To address the question of the behaviour of metal oxide nanoparticles when they come into contact with
natural colloids (1-1000 nm), a number of laboratory experiments and measurements were conducted by
looking at particle size under different pH and humic substance concentrations.
Experiments were conducted on synthesized iron oxide (hematite) particles (by hydrolysis of iron
chloride in dilute HCl at 106 °C) (Kendall et al., 2004; Matijevic & Scheiner, 1978) of about 6 nm
characterised by transmission electron microscopy (TEM), 9 nm by flow-field flow fractionation (FlFFF)
and 16 nm by dynamic light scattering (DLS). Characterisation by FlFFF dilutes samples approximately
1000 times, challenging limits of detection by UV absorbance. FeOx was used at concentrations of 200
mg L-1, iron. Resulting FeOx nanoparticles were charge-stabilized and did not require further stabilization
and used without further modification. FeOx nanoparticles were then mixed with varying concentrations
(0-25 mg L-1) of fulvic acid and peat humic acid. This solution was characterised between pH 2 and pH 5
by FlFFF and from pH 2 to pH 10 -12 for analysis by DLS to determine the particle size and aggregation
properties. Electrophoretic mobilities (charge measurements) were conducted on all the solutions and
point of zero charge was found to be at pH 7 for the FeOx, lowered by the presence of Cl- ions.
Measurements were carried out across the entire pH range, there are some examples such as acid mine
drainage have waters as low as pH 2 and some natural system have waters as low as pH 3.5.

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 U21 POSTGRADUATE RESEARCH CONFERENCE PROCEEDINGS I
Water - how need drives research and research underpins solutions to world-wide problems
20th-25th July 2008, University of Birmingham, Birmingham UK

Results and discussion

Results are in agreement with Cromeries et al (2002) for hematite and Baalousha et al (2008) for FeOx
with humic acid. Particle size increased with increase in pH (from pH 2-7) and with an increase in organic
matter with particle aggregation occurring between pH 5.5 and pH 9 which coincides with the point of zero
charge of the iron oxide occurring at pH 7 with maximum particle size of 8 µm. This is due to 1) a
decrease in charge on the Fe oxide particles allowed particle growth by coagulation and aggregation; and
2) by dissolved Fe3+ adsorption occurring onto the particles; or, 3) by the humics forming a surface layer
around the particle and shielding the charge.
The increase in size with humics acid may indicate that some stability may occur in the water
column allowing some degree of transportation before sedimentation would occur.
Once as sediment in the benthic layer, exposure to most aquatic organisms would be limited, unlike the
bottom benthic feeders. This work reflects the possibilities of the fate and transportation of other, metal
oxide nanoparticles that may end up in the aquatic systems as pollutants.

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 U21 POSTGRADUATE RESEARCH CONFERENCE PROCEEDINGS I
Water - how need drives research and research underpins solutions to world-wide problems
20th-25th July 2008, University of Birmingham, Birmingham UK

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