Challenges and Opportunities of Nanomaterials in Drinking Water

[Project #4311]
ORDER NUMBER: 4311
DATE AVAILABLE: May 2011
PRINCIPAL INVESTIGATORS:
Mary Ellen Tuccillo, Glen Boyd, Dionysios Dionysiou, and Jo Anne Shatkin
OBJECTIVES:
The objective of this project was to provide drinking water utilities with information on
the state of knowledge regarding nanomaterials in the environment and to identify
knowledge gaps, with special attention to issues relevant to drinking water. Numerous
technical issues surround nanomaterials, and this report was intended to touch on an array
of topics that include information about nanomaterials, health effects, fate and transport
in the environment, detection methods, potential for removal during drinking water
treatment, and the potential for beneficial use in drinking water treatment and water
quality monitoring.
SUMMARY OF RESULTS AND DATA GAPS:
The amount of available literature on nanomaterials is large with much of it focused on
development and applications. Of particular interest to the drinking water, wastewater,
and environmental communities is ongoing research on the potential uses for water
treatment. Despite the proliferation of research, work is still needed in several areas
pertaining to environmental impacts and health effects. Below are some highlights of this
literature review.
(1) What are nanomaterials?
Nanomaterials comprise a diverse set of substances that are generally defined by particle
size: they have at least one dimension that measures less than 100 nm. The term
nanomaterial includes both nanoparticles (discrete nano-sized particles) and
nanostructured materials (with nano-sized surface topography or other features). They
may be naturally occurring (e.g., iron oxyhydroxides, amorphous silica, clay minerals,
viruses), inadvertently generated, such as soot from combustion, or engineered. Examples
of engineered nanomaterials include nanosilver (n-Ag), nano titanium dioxide (nanoTiO2), cerium oxide, fullerenes (all-carbon molecules such as buckyballs, and carbon
nanotubes), and quantum dots.
Their tiny size bestows nanomaterials with properties that differ from those of larger
particles. These properties include a large surface-area-to-mass ratio, increased reaction
kinetics, disinfectant capabilities, and optical and electrical properties. The very smallest
engineered nanoparticles (quantum dots) exhibit quantum effects and can be used as
semiconductors. Their special properties make nanomaterials attractive for many
applications, ranging from cosmetics to medicine. In recent years, the manufacture and

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use of nanomaterials has increased tremendously and spans a wide range of products. Our
understanding of health and environmental effects, however, has not caught up with this
level of technological development.
(2) How can I determine whether they exist in my source water?
Data on environmental occurrence of nanomaterials are lacking. Releases to the
environment may occur via point sources (releases from manufacturing plants,
wastewater treatment plant effluent) or non-point runoff (e.g., wear and tear of
nanomaterial-based products). To understand whether engineered nanomaterials are
present in source waters at concentrations that should cause concern, sampling and
analysis of surface waters, wastewater treatment plant effluents, and soils is needed.
Groundwater sampling may be appropriate if nanomaterials have been used in subsurface
remediation.
Many methods have been used to characterize nanomaterials in industrial and research
settings. Useful properties to measure include, but are not limited to, particle size
distribution, concentration, morphology, state of aggregation, and chemical composition.
To be useful, methods for detection and analysis of nanoparticles in environmental media
need to have low detection limits and enable the distinction between natural and
engineered nanoparticles. Examples of methods that show promise for water samples
include scanning electron microscopy (SEM) and transmission electron microscopy
(TEM) to determine nanoparticle morphology, size, and identity. Separation methods
such as flow field-flow fractionation followed by a sensitive detection method such as
inductively-coupled mass spectrometry (ICP-MS) have been used for quantification and
chemical analysis of nanoparticles in water. Continued research is needed for methods
that can be used for routine monitoring and that minimize artifacts from sample
preparation.
(3) What are potential human health concerns?
Because nanomaterials are diverse, generalizations about toxicological effects cannot be
made. Most studies in the literature involve inhalation exposure; studies of dermal and
ingestion pathways are relatively few. However, absorption across the gut has been
reported, and nanoparticles have been found to distribute in the body. Existing data
suggest that some nanomaterials cause adverse health effects, but data are too limited to
draw general conclusions. Some of the ongoing research needs include identifying which
metrics to use in toxicology studies and conducting experiments at environmentally
relevant concentrations. A mass-based dose might not be the right metric; basing
measurements on other properties such as total surface area may be more appropriate.
(4) What affects fate and transport of nanomaterials in the environment?
Environmental fate and transport of nanomaterials that have been released into the
environment will depend on a number of processes, such as aggregation, adsorption,
abiotic degradation (photolysis or hydrolysis), and microbially-mediated changes (e.g.,

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interactions of microbes with surface coatings). Nanomaterials, both engineered and

natural, may adsorb and serve as transport vehicles for other contaminants. Particular
attention should be paid to aggregation because it increases particle size and can result in
sedimentation or filtration, removing nanoparticles from the water column. Aggregation
is controlled by both the surface characteristics of the particles and the water chemistry
(ionic strength, dissolved organic carbon, ionic composition). Much of what is
understood about environmental fate processes for nanoparticles is derived from
experience with colloid chemistry. Continued research is needed on these various
processes for the different types of nanomaterials.
(5) Will they be removed during drinking water treatment?
Most common drinking water treatment processes are not designed specifically to remove
nanoparticles. However, some removal may occur, and aggregation makes removal more
likely. Alum coagulation can remove some portion of nanoparticles, with the presence of
natural organic matter playing an important role in this process. Studies are lacking on
the ability of membranes to remove nanoparticles, but aggregated nanoparticles are likely
to be removed by microfiltration, and reverse osmosis and nanofiltration would be
expected to remove nanoparticles. Removal by ion exchange is possible, but currently
unexplored. Given the paucity of published literature on removal of nanoparticles during
drinking water treatment, predictions are largely speculative.
(6) What are potential applications?
Many of the characteristics that make engineered nanomaterials useful for industrial
purposes also present opportunities for drinking water treatment. Research is underway
on different types of processes. One is the tailoring of membranes for specific needs, such
as removal of metals and organics or disinfection. Examples include nanoreactive
membranes endowed with nanomaterials to improve selectivity and capacity or to
provide disinfection capabilities. Materials such as zeolites, carbon nanotubes, or
mesoporous membranes with monolayers can serve as sorbents for organic compounds,
metals, and radionuclides. TiO2 can function as both an oxidative and reductive catalyst.
When used with light, nano-TiO2 can photocatalytically oxidize organic compounds.
These nanomaterial-based processes are in the development stage, and challenges remain
before they will be ready for full-scale deployment, although some are also being
investigated for point-of-use treatment. If they can be brought to full-scale use, they
would offer opportunities for removal of trace and emerging contaminants.
Nanomaterials are also being researched for use as nanosensors for water testing. Taking
advantage of the optical and electrochemical properties of quantum dots and nanosized
gold, researchers are developing methods for detecting various environmental
contaminants such as metals and algal toxins. These sensors are appealing for their low
detection limits and good selectivity.

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(7) What regulatory developments are there?

The need for regulation is acknowledged by countries with strong nanotechnology
industries, including the United States. There are, however, several challenges.
Regulators must make decisions while there are still knowledge gaps in topics such as
exposure and health effects. From an institutional standpoint, there are several agencies
that might regulate nanomaterials, including the USEPA, the Food and Drug
Administration, and the Department of Labor. The two most common approaches to
addressing the lack of nanomaterials regulation are to extend existing regulations and to
establish voluntary initiatives.
The USEPA is currently pursuing regulatory options for nanomaterials under three
different provisions of the Toxic Substances Control Act (TSCA). In particular, the
Significant New Use Rule (SNUR) allows USEPA to require the prevention of releases to
water of materials that are new substances or existing substances with new uses. In
September 2010, USEPA issued a SNUR for carbon nanotubes. At the state level,
California and Wisconsin have begun developing state regulations. Internationally,
Australia, Canada, the European Union, Japan, and the United Kingdom are working on
regulation of nanotechnologies.

2011 Water Research Foundation. ALL RIGHTS RESERVED.