1-s2.0-S0956053X09004607-main

Waste Management 30 (2010) 504520
Contents lists available at ScienceDirect
Waste Management
journal homepage: www.elsevier.com/locate/wasman
Engineered nanoparticles in wastewater and wastewater sludge Evidence

and impacts
Satinder K. Brar a,*, Mausam Verma b, R.D. Tyagi a, R.Y. Surampalli c
a
INRS-ETE, Universit du Qubec, 490, Rue de la Couronne, Qubec, Canada G1K 9A9
Department of Biological Engineering, Sexton Campus, Dalhousie University, Halifax, Nova Scotia, Canada B3J 2X4
c
US Environmental Protection Agency, P.O. Box 17-2141, Kansas City, KS 66117, USA
b
a r t i c l e
i n f o
Article history:
Accepted 20 October 2009
Available online 17 November 2009
a b s t r a c t
Nanotechnology has widespread application in agricultural, environmental and industrial sectors ranging
from fabrication of molecular assemblies to microbial array chips. Despite the booming application of
nanotechnology, there have been serious implications which are coming into light in the recent years
within different environmental compartments, namely air, water and soil and its likely impact on the
human health. Health and environmental effects of common metals and materials are well-known, however, when the metals and materials take the form of nanoparticles consequential hazards based on
shape and size are yet to be explored. The nanoparticles released from different nanomaterials used in
our household and industrial commodities nd their way through waste disposal routes into the wastewater treatment facilities and end up in wastewater sludge. Further escape of these nanoparticles into
the efuent will contaminate the aquatic and soil environment. Hence, an understanding of the presence,
behavior and impact of these nanoparticles in wastewater and wastewater sludge is necessary and
timely. Despite the lack of sufcient literature, the present review attempts to link various compartmentalization aspects of the nanoparticles, their physical properties and toxicity in wastewater and wastewater sludge through simile drawn from other environmental streams.
2009 Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
4.
5.
6.
7.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Nanoparticle toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Application of nanomaterials in decontamination of organic compounds potential source in wastewater and sludge. . . . . . . . . . . . . . . . . . .
3.1.
Physical regime of nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Do nanoparticlenanoparticle interactions produce free nanoparticles?. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Are particles desired in wastewater treatment plants? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Pertinence of nanoparticles in wastewater and wastewater sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Preliminary treatment bar screens and grit removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.1.
Primary treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Secondary treatment process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.1.
Role of physical interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.2.
Interaction with microorganisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.3.
Biodegradation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.4.
Interaction with other pollutants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Transport during land application and/or landfilling of wastewater sludge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Fate in soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2.
Fate in water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.
Interactions with plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Future outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
* Corresponding author. Tel.: +1 418 654 3116; fax: +1 418 654 2600.
E-mail address: satinder.brar@ete.inrs.ca (S.K. Brar).
0956-053X/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2009.10.012
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S.K. Brar et al. / Waste Management 30 (2010) 504520
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 517
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 517
1. Introduction
Burgeoning human population has put immense pressure on
the consumer products. In order to meet the ever growing needs
of the society, nanotechnology has touched many spheres of utility
services, including consumer products, health care, transportation,
energy and agriculture (Taton et al., 2002; Cui et al., 2001). Nanotechnologies allow the production and manipulation of minute objects that measure as little as one billionth of a meter (the
nanometer). Nanotechnologies got started in the early 1980s with
the appearance of a new type of microscope (atomic force microscope), which allowed not only the observation of units of atoms
and molecules, but also their physical manipulation and the relative scale of comparison as presented in Fig. 1. In 1991, the manipulation of carbon atoms, arranged in the form of a tube, made it
possible to create the rst nanotube six times lighter than steel,
but 100 times stronger. The nanomaterials form three types of
architecture according to the end use are presented in Table 1.
The increased use of nanomaterials introduces the nanoparticles intentionally/unintentionally into the waste streams, viz.
wastewater treatment facilities. A list of daily use nanomaterials
and corresponding nanoparticles is presented in Table 2. The impact that wastewater treatment has on nanomaterials, or conversely, the impact that nanomaterials have on wastewater
treatment, is largely unknown. Moreover, questions remain on
the efcient way to remove these nanoparticles from industrial
wastewaters and sewage treatment plants. Recent research sug-
gests that some nanoparticles escape from treatment plants and

are discharged into natural water bodies. These nanoparticles can
remain in the environment for long periods and can be potentially
toxic to the aquatic life (Oberdrster, 2004; Velzeboer et al., 2008).
Upon release, nanomaterials are likely to interact with aquatic surfaces and biological species as well as aggregate, depending on the
interplay between electrostatic and van der Waals interactions
(Thess et al., 1996; Saleh et al., 2008).
At this juncture, there is an urgent need to analyze the possible
behavior and fate of nanoparticles in wastewater treatment facilities and wastewater sludge. There is an extreme paucity of literature in this eld as evident from Fig. 2 which illustrates various
publications in the eld of nanoparticles drawn from different research journals. Hence, the review discusses the peer-reviewed literature published so far addressing the issues and raising
questions on the potential impact of these nanoparticles. Sometimes, the statements are based on extrapolation from non-wastewater based processes to wastewater processes, however, sound
evidence has been provided in this regard. The review takes into
consideration only the anthropogenic nanoparticles, also called,
engineered nanoparticles (as given in Table 1), as natural nanoparticles have been already studied and reviewed in details elsewhere.
2. Nanoparticle toxicity
The nanomaterials possess large surface area per unit of volume
which lends novel electronic properties relative to conventional
Fig. 1. Comparison of nanoparticles with macroscale particles (Modied from: National Nanotech Initiative, US EPA White paper, 2005).
Table 1
Different forms of nanoscale architecture.
3D
2D
1D
Fullerenes
Carbon nanotubes and

nanolaments
Metal and magnetic nanowires
Oxide and carbide nanorods
Semiconductor quantum wires
Nanolaminated or compositionally modulated

materials
Grain boundary lms
Clay platelets
Semiconductor quantum wells and superlattices
Magnetic multilayers and spin valve structures
LangmuirBlodgett lms
Colloidal particles
Nanoporous silicon
Activated carbons
Nitride and carbide precipitates in high-strength low-alloy steels
Semiconductor particles in a glass matrix for non-linear optical
components
Semiconductor quantum dots (self-assembled and colloidal)
Quasi-crystals
Silicon inversion layers in eld effect transistors

Paints, rusts in pipes
506
Table 2
Production of nanoparticles from different sources and respective applications.
Source
Type of nanoparticle
Quantity used in
terms of tons
Application/uses
Metals and alkaline

earth metals
Ag
Fe
Pt group metals
Sn
Al
Cu
Zr
Se
Ca
Mg
High
High
High
Unknown
High
Unknown
High
Low
Low
Low
Antimicrobials, paints, coatings, medical use, food packaging

Water treatment
Catalysts
Paints
Metallic coating/plating
Microelectronics
Nutraceuticals, health supplements
Metal oxides
TiO2
ZnO
CeO2
SiO2
Al2O3
High
Low
High
High
Low
Cosmetics, paints, coatings

Cosmetics, paints, coatings
Fuel catalyst
Paints, coatings
Usually substrate bound, paintings
Carbon materials
Carbon black
Carbon nanotubes
Fullerenes (C60-C80)
High
MediumHigh
MediumHigh
Substrate bound, but released with tyre wear

Used in a variety of composite materials
Medical and cosmetics use
Miscellaneous
Nanoclay
Ceramic
Quantum dots
Organic nanoparticles
High
High
Low
Low
Plastic packaging
Coatings
Different compositions
Vitamins, medicines, carriers for medicines and cosmetics, food
additives and ingredients
Safety of Manufactured Nanomaterials: About, UOECD Environment Directorate, OECD.org, 18 July 2007 <http://www.oecd.org/about/0,3347,en_2649_37015404_
1_1_1_1_1,00.html>. Small Sizes that Matter: Opportunities and Risks of Nanotechnologies, Joint report of the Allianz Center for Technology and the OECD International
Futures Programme, ed. Dr. Christoph Lauterwasser, OECD.org 18 July 2007 <http://www.oecd.org/dataoecd/37/19/37770473.pdf>.
3500
No. of publications
3000
79.3 %
2500
2000
1500
1000
14.8 %
500
0.6 %
4.9 %
0.4 %
0
Synthesis
Air
Wastewater
Toxicity
Environmental Wastewater
Remediation
sludge
Biosolids
Fields of publication
Fig. 2. Number of publications in different disciplines of nanoparticles, until December 2008. (Note, the number of publications for the possibility of nanoparticle
contamination in wastewater sludge are really minimal, top includes percent of the publications; it is a collective survey done on science direct website for different journals
and hence the publications thereof; Water Research, Water, Science and Technology, Chemosphere, Biochemical and Biophysical Research Communications, Waste
Management, Air, Water and Soil Pollution, Journal of Environmental Quality, Aquatic Toxicology, Water Environment Research, Journal of Hazardous Materials.)
chemicals. These special properties that make nanomaterials useful may also cause some nanomaterials to pose hazards to humans
and the environment, under certain conditions. A number of
authors have published literature on characterization, fate, and
toxicological information of nanomaterials and proposed research
strategies for evaluation of safety of nanomaterials (Dunford
et al., 1997; Morgan, 2005; Holsapple et al., 2005; Thomas and
Sayre, 2005; Balshaw et al., 2005; Tsuji et al., 2006; Borm et al.,
2006; Powers et al., 2006; Franklin et al., 2007; Kennedy et al.,
2008) and hence this does not form major part of this review.
The major toxicological concern is the fact that some of the manufactured nanomaterials are redox active (Colvin, 2003), and others
are transported across cell membranes and especially into mito-
chondria (Foley et al., 2002). Lam et al. (2004) demonstrated that

carbon nanotube products induced dose-dependent epithelioid
granulomas in mice and, in some cases, interstitial inammation
in the animals of the 7-day post-exposure groups. Oberdrster
(2004) indicated that nanomaterials (Fullerenes, C60) induced oxidative stress in a sh model. Hence, toxicity of nanoparticles that is
coming to the fore is posing questions on the sustainability and future of nano-products. An in-depth critical review in this context
has been recently published by Klaine et al. (2008) discussing the
key aspects of their fate, behavior, disposition, and toxicity, with
a particular focus on manufactured nanomaterials. Brunner et al.
(2006) reported nanoparticle-specic cytotoxic mechanism for uncoated iron oxide and partial detoxication or recovery after
Table 3
Nanoparticle toxicity of different nanomaterials.
Test organisms
Effects
Comments
References
Titanium dioxide (TiO2), silicon

dioxide (SiO2), and zinc oxide
(ZnO) water suspensions
Gram-positive Bacillus subtilis and Gramnegative Escherichia coli
The three photosensitive nanomaterials were

harmful to varying degrees, with antibacterial
activity increasing with particle concentration;
Bacillus subtilis being highly susceptible
There is a need for caution during the use

and disposal of such manufactured
nanomaterials to prevent unintended
environmental impacts, as well as the
importance of further research on the
mechanisms and factors that increase
toxicity to enhance risk management.
US EPA, 2005; Adams et al.,

2006
Silver (Ag), molybdenum (MoO3),

aluminum (Al), iron oxide (Fe3O4),
titanium dioxide (TiO2) and
Tungsten (W)
Cellular morphology, mitochondrial

function, membrane leakage of lactate
dehydrogenase, reduced glutathione
levels, reactive oxygen species, and
mitochondrial membrane potential of rat
liver cells
Ag was highly toxic whereas, MoO3 moderately

toxic and Fe3O4, Al, MnO2 and W displayed less
or no toxicity at the doses tested. Exposed cells
at higher doses became abnormal in size,
displaying cellular shrinkage, and an
acquisition of an irregular shape.
Cellular response to nanosized particle

exposure in rat liver cells clearly give an
indication of similar possibility in human
cells
Hussain et al., 2005
Multi-walled carbon nanotube,

aluminum, alumina, zinc, and zinc
oxide
Seed germination and root growth of

higher plant species (radish, rape,
ryegrass, lettuce, corn, and cucumber)
Results are signicant in terms of use and

disposal of engineered nanoparticles
Lin and Xing, 2007
Uncoated fullerenes
Fish brain tissue
Inhibition on root growth varied greatly among

nanoparticles and plants. Suspensions of
2000 mg/L nano-Zn or nano-ZnO practically
terminated root elongation of the tested plant
species
Nanomaterials oxidative stress and caused
severe lipid peroxidation in sh brain tissue
C60 fullerene
A mixture of nanoscale SiO2 (nanoSiO2) and TiO2(nano-TiO2)
Salmonella thyphimurium
Soybean (Glycine max)
Oberdrster, 2004;
Oberdrster et al., 2005;
Moore, 2006
Babynin et al., 2002
Lu et al., 2002
Uncoated alumina particles
Corn, cucumber, soybean, cabbage and

carrot
Ultrane ambient particulate

suspensions; polystyrene
nanoparticles; quantum dots and
single-wall carbon nanotubes
Rat alveolar epithelial cells
Nano-C60, a fullerene aggregate
Classic engineered nanomaterial (nanoC60) contribute to the cytotoxicity
Sayes et al., 2005
Gold nanoparticles
Human dermal broblasts, human liver

carcinoma cells (HepG2), and neuronal
human astrocytes
Single-donor fresh semen
Disruption of alveolar epithelial barrier

properties due to apical nanoparticle exposure
likely involves alteration of cellular transport
pathways and is dependent on specic
nanoparticle composition, shape and/or
surface charge.
Disrupts normal cellular function through lipid
peroxidation; reactive oxygen species are
responsible for the membrane damage
Sperm became non-motile
Possible and fugitive release of

nanomaterials into the aquatic
environment needs to be controlled
Despite aiding in the absorption and

assimilation of nutrients, these
nanoparticles nally inhibited
germination and plant growth
These studies further triggered the
interest to explore the negative effect of
nanoparticles on plants
Possibility of contribution to deleterious
effects on human health
Wiwanitkit et al., 2007
C60-nanoparticles (Buckminster
fullerenes)
Algae (Pseudokirchneriella subcapitata) and

crustaceans (Daphnia magna)
On interaction with other organic compounds,

the toxicity was magnied
Water-soluble fullerene (nC60)
Daphnia magna and adult male fathead

minnow, Pimephales promelas
Induction of lipid peroxidation in brain, in gill,

and signicantly increased expression of CYP2
family isozymes in liver as compared to control
sh
Spermatotoxicity of the gold nanoparticle

can be detected
The inherent toxicity of manufactured
nanoparticles, and interactions with other
compounds and characterization of
nanoparticles in aqueous suspension are
of importance for risk assessment of
nanomaterials
Acute toxicity of nanomaterials in aquatic
organisms is highly evident
Antimutagenic
Increases nitrate reductase, enhances its
abilities of absorbing and utilizing water and
fertilizer, stimulate its antioxidant system, and
apparently hasten its germination and growth
Inhibited root elongation
Yang and watts, 2005;

Murashov, 2006
Yacobi et al., 2007
Type of nanoparticles
Baun et al., 2007
Zhu et al., 2006
507
508
treatment with zirconia, ceria, or titania. Likewise, Rothen-Rutishauser et al. (2006) combined different microscopic techniques to
visualize ne and nanoparticles in red blood cells: (I) uorescent
particles by laser scanning microscopy combined with digital image restoration, (II) gold particles by conventional transmission
electron microscopy and energy ltering transmission electron
microscopy, and (III) titanium dioxide particles by energy ltering
transmission electron microscopy. By using these differing microscopic techniques particles 60.2 lm and nanoparticles in red blood
cells were detected. The authors reported that surface charge and
the material of the particles did not inuence their entry. These results suggested that particles may penetrate the red blood cell
membrane by an unknown mechanism different from phagocytosis and endocytosis. Toxicity of nanoparticles was manifested by
inammation probably resulting from oxidative stress.
Gatti is the authority on nanopathology who discovered the effect of nanoparticles on human health for the rst time. The author
henceforth reported several effects of the engineered nanoparticles
on human health, including effects on colon, blood, endothelial cell
function, muscles, skin, sarcoma development (Gatti and Rivasi,
2002; Gatti, 2004, 2005; Gatti et al., 2004, 2008; Sabbioni et al.,
2004; Peters et al., 2004; Hansen et al., 2006; Cross et al., 2007).
Antimony trioxide nanoparticles have been found to affect the human hematopoietic progenitor cells at 5 lg/ml concentration (Bregoli et al., 2009. A study examined the relationship between a
group of workers experiencing vague symptoms in relation to
the nanoparticle exposure (Song et al., 2009; Gilbert, 2009). Polyacrylate, comprising nanoparticles, was conrmed in the workplace.
Pathological examinations of patients (in this case, seven young
females, 1847 years) lung tissue displayed nonspecic pulmonary
inammation, pulmonary brosis and foreign-body granulomas of
pleura, thus conrming chronic toxicity of the nanoparticles on
lungs. However, there are some unanswered questions in this
study especially pertaining to the type of nanoparticle, their concentration and as to if they were the true initiators and also the statistical count is not signicant enough to make a real-time
conclusion.
Nanosceptics even nd certain similarities between nanoparticles and carbon nanotubes, one of the most popular nanoparticles,
and asbestos bers. In view of a rapid development of nanotechnologies, it is essential to establish adequate criteria for risk assessment that could protect against potential harmful effects arising
from specic properties of substances occurring in the form of
nanoparticles. The ecotoxicological data of various products of daily use, considered to be potential source of nanoparticles, suggest
varied toxicity of different nanoparticles as enumerated in Table 3.
The toxicity of certain well-known metals and metal oxide nanoparticles is known and understood. However, there is still scarcity
of literature on many of the aquatic and more particularly terrestrial organisms which may bring in new information on the potential interaction of these nanoparticles. More efforts in this direction
would bridge the knowledge gap as there is a transition from terrestrial to aquatic environment. Such information would also prove
handy for regulatory agencies to determine the threshold limits of
these nanoparticles.
3. Application of nanomaterials in decontamination of organic

compounds potential source in wastewater and sludge
Nanomaterials have been extensively used for rapid or costeffective cleanup of wastes when compared to current conventional approaches (Shan et al., 2009). The application benets are
derived from the nanoparticle characteristics: enhanced reactivity,
surface area, sub-surface transport, and/or sequestration characteristics of nanomaterials.
Research has shown that nanoscale iron particles are very effective for the transformation and detoxication of a wide variety of
common environmental contaminants, such as chlorinated organic
solvents, organochlorine pesticides, and polychloro biphenyls (Elliott and Zhang, 2001; Zhang, 2003; Glazier et al., 2003; Ivanov et al.,
2004; Quinn et al., 2005; Mauter and Elimelech, 2008). Modied
iron nanoparticles, such as catalyzed and supported nanoparticles
have been synthesized to further enhance the rate and efciency of
remediation with recent developments in both laboratory and pilot
studies, including: (1) synthesis of nanoscale iron particles (10
100 nm, >99.5% Fe) from common precursors such as Fe(II) and
Fe(III); (2) reactivity of the nanoparticles towards contaminants
in soil and water over extended periods of time (e.g., weeks); (3)
eld tests validating the injection of nanoparticles into aquifer,
and (4) in situ reactions of the nanoparticles in the sub-surface.
In addition to the zero-valent iron, other nanosized materials,
such as metallo-porphyrinogens have been tested for degradation
of tetrachlorethylene, trichloroethylene, and carbon tetrachloride
under anaerobic conditions (Dror et al., 2005). Titanium oxide
based nanomaterials have also been developed for potential use
in the photocatalytic degradation of various chlorinated compounds (Chen et al., 2005). Enhanced retention or solubilization
of a contaminant may be helpful in a remediation setting. Nanomaterials may be useful in decreasing sequestration of hydrophobic
contaminants, such as polycyclic aromatic hydrocarbons (PAHs),
bound to soils and sediments. The release of these contaminants
from sediments and soils could make them more accessible to
in situ biodegradation; however, the fate of nanoparticle bound organic compounds is still a puzzle. Nanomaterials made from
poly(ethylene) glycol modied urethane acrylate have been used
to enhance the bioavailability of phenanthrene (Tungittiplakorn
et al., 2005). In fact, various magnetic nanoparticles have been prepared by chemical co-precipitation method and used for the removal of Cr(VI) from synthetic electroplating wastewater
encompassing excellent adsorbent capacities (Hu et al., 2007).
Literature is abundant with studies on utilization of nanoparticles for adsorption of various pollutants, mostly metals and dyes
(Dai et al., 1999; Hu et al., 2005; Chin et al., 2006; Messina et al.,
2006; Huang et al., 2007; Li et al., 2007a; Wang, 2007; Blaney
et al., 2007; Xu et al., 2007a,b). Nanoparticles, such as poly(amidoamine) dendrimers can serve as chelating agents, and can further
enhance ultraltration of a variety of metal ions (Cu(II), Ag(I),
Fe(III), and others) by attaching to functional groups, such as primary amines, carboxylates, and hydroxymates (Diallo et al.,
2005). Arsenite and arsenate have been precipitated in the subsurface using zero-valent iron, making arsenic less available (Kanel
et al., 2005). At this crux, the point to be investigated is the role of
nanoparticles on adsorption to the pollutants in secondary pollution, which is going to be another reality in the future (discussed
later).
Currently, about 150% of nitrogen required for plant uptake is
applied as fertilizer (Frink et al., 1999). Fertilizers and pesticides
that incorporate nanotechnology may result in less agricultural
and lawn/garden runoff of nitrogen, phosphorous, and toxic substances, which is potentially an important emerging application
for nanotechnology. These potential applications are still in the
early research stage (World Resources Institute, 2000; OECD,
2001; USDA, 2003). Applications involving dispersive uses of
nanomaterials in wastewater might have far reaching implications
on aquatic life and humans (Rao et al., 2004; Brar et al., 2009).
Nanotechnology does possess the potential to improve the environment, both through direct applications of nanomaterials to detect, prevent, and remove pollutants, as well as indirectly by using
nanotechnology to design cleaner industrial processes and create
environmentally responsible nano-products. However, in this pursuit of efcient clean-up of the environmental compartments,
some of these nanoparticles are being deliberately loaded into the

environment also comprising wastewater and down the line, will
end up in soils, sediments, water nally posing their way into
the ora and fauna via food chain. To begin with, it is imperative
to understand the physical regime of nanoparticles and inter-particle interactions which govern their overall behavior in the wastewater treatment plants.
509
small clusters are completely different from the better known

property of each component in the bulk or at extended surfaces.
This situation would also arise in wastewater treatment plants
where the nanoparticles can be present in different forms. Moreover, complex quantum mechanical models are required to predict
the evolution of such properties with particle size, and typically
very well dened conditions are needed to compare experimental
and theoretical predictions.
3.1. Physical regime of nanoparticles

The principal parameters of nanoparticles are their shape
(including aspect ratios where appropriate), size, and the morphological sub-structure. Nanoparticles are present as an aerosol
(mostly, solid or liquid phase in air), a suspension (mostly, solid
in liquids) or an emulsion (two liquid phases) (Anon, 2003). In
the presence of chemical agents (surfactants), the surface and
interfacial properties can be modied. Such agents can indirectly
stabilize against coagulation or aggregation by conserving particle
charge and by modifying the outmost layer of the particle (can
happen during various steps of wastewater treatment plants as
there is frequent use of coagulants and polyelectrolytes for solids
removal). Depending on the growth history and the lifetime of a
nanoparticle, very complex compositions, possibly with complex
mixtures of adsorbates (for instance, in this case, it can be wastewater sludge), are expected. Research suggests that carbon-based
nanoparticles adsorb to materials commonly used in wastewater
systems. Duncan et al. (2008) reported that fullerenes can adsorb
to natural organic matter. The natural organic matter caused disaggregation of nC60 crystals and aggregates under typical solution
conditions of natural water, leading to signicant changes in particle size and morphology (Steven et al., 2001; Xie et al., 2008). Such
effects magnied with increasing natural organic matter concentration and it may act as a carrier in the transport and toxicity of
C60 in waste streams. Organic matter is commonly found in
domestic wastewater in the form of suspended and dissolved solids (humic and fulvic acids). Consumer products, and debris and
could also be expected to sorb on these nanoparticles. Another aspect of nanoparticle fate in wastewater is that fullerenes have the
potential to sorb to organic contaminants, such as naphthalene
(Cheng and Tomson, 2005). While naphthalene is commonly
known as a gasoline contaminant and is unlikely to surface in
wastewater, the nding nonetheless demonstrates that carbonbased nanoparticles could sorb to other contaminants which, if
not removed during wastewater treatment, could be discharged
with the efuent into the environment. Although no direct studies
have been reported on sorption of nanoparticles onto biolms lining pipe walls as well as basins within the treatment plant, still
previous studies on particle entrapment in biolms are a sound
proof for the same. No data was also reported regarding the sorption of other types of nanoparticles to infrastructure materials.
At the nanoparticleliquid interface, polyelectrolytes have been
utilized to modify surface properties and the interactions between
particles and their environment. They have been used in a wide
range of technologies, including adhesion, lubrication, stabilization, and controlled occulation of colloidal dispersions (Liufu
et al., 2004). Polyelectrolytes have been used for decades in wastewater treatment plants (Verma et al., 2006) which eventually end
up in wastewater sludge and might suffer similar fate. Hence,
nanoparticles in wastewater might encounter change in charge
dispersion due to interaction with polyelectrolytes and thus contribute to a completely changed behavior.
At some point between the Angstrom level and the micrometre
scale, the simple picture of a nanoparticle as a ball or droplet
changes. Both physical and chemical properties are derived from
atomic and molecular origin in a complex way. For example, the
electronic and optical properties and the chemical reactivity of
3.2. Do nanoparticlenanoparticle interactions produce free

nanoparticles?
At the nanoscale, particleparticle interactions are either dominated by weak Van der Waals forces, stronger polar and electrostatic interactions or covalent interactions. Particle aggregation is
determined by the inter-particle interaction, depending on the viscosity and polarizability of the uid. For nanoparticles in liquids,
particle charge can be stabilized by electrochemical processes at
surfaces (Huber et al., 1996; Selvan et al., 1999). The nanoparticlenanoparticle interaction forces and nanoparticleuid interactions play a key role in describing physical and chemical processes,
and the temporal evolution of free nanoparticles (will be the case
in nanoparticlewastewater interactions). However, they are difcult to characterize due to the small amount of molecules actually
present on the surface active layer. Surface energy, charge and solvation are additional relevant parameters to be considered. Due to
the critical role of the nanoparticlenanoparticle interaction and
the nanoparticleuid interaction, the term free nanoparticle can
be easily misunderstood. The interaction forces, either attractive
or repulsive, crucially determine the fate of individual and collective nanoparticles (Gomoll et al., 2000; McManus et al., 2000). This
interaction between nanoparticles may form aggregates and/or
agglomerates that inuence the real behavior (Akane et al.,
1990). In gas suspensions, aggregation is crucially determined by
the size and diffusion, and coagulation typically occurs faster than
in the liquid phase as the sticking coefcient is closer to unity than
in liquids. The former can occur in the case of digestion processes
which are used for processing wastewater sludge so that the biogas
that is formed might contain the nanoparticle in the coagulated
form resulting in secondary pollution of air besides presence in
wastewater.
3.3. Are particles desired in wastewater treatment plants?
Particles represent undesired pollutants in most of the process
waters. Apart from the mass of suspended matter which is often
used as bulk parameter, many other quality indicators are strongly
associated with particles, such as hygienic contaminants and adsorbed chemicals. On one hand, particles may negatively interfere
in various treatment processes and supply systems, while particulate matter in the form of biomass is a necessary prerequisite in the
unit operations involving secondary treatment steps (Wang et al.,
2005). Nevertheless, the removal of particulate matter will be
one of the most crucial steps in water and wastewater treatment.
In order to understand the behavior of particles in water and
wastewater and to develop and design efcient treatment facilities,
the characteristics of particles have to be known on the basis of
individual solids and whole particle populations. In wastewater
treatment, particles are of extremely heterogeneous nature with
respect to size, density, shape, chemical composition, shear
strength, surface charge, etc. which represents information that
is in most cases not precisely available. Fig. 3 represents the schematic of a typical wastewater treatment plant tracing the fate of
nanoparticles all the way from the source through the unit operations and nally to the sink, aquatic streams.
510
To begin with, how do these nanoparticles nd their way into

wastewater treatment plants? Source of nanomaterials principally
originate from the collection systems in municipalities where huge
amounts of nanoparticles are released daily as seen in Table 4. This
Table represents per capita usage in European scenario, but this is
also a worldwide phenomenon. The presented data clearly mentions the gravity of nanopollution that is being caused by the daily
activities. The scenario will be more severe if industrial use data is
appended to it. Engineered nanoparticles have been on the market
for some time and are commonly used in cosmetics, sporting
goods, tires, stain resistant clothing, sunscreens, toothpaste, food
additives, and others (Colvin, 2003; Product inventory, 2007).
These nanomaterials, and new more deliberately fabricated nanoparticles, such as carbon nanotubes, constitute a small minority
of environmental nanomaterials. In fact, the quantity of man-made
nanoparticles ranges from well-established multiton per year production of carbon black (for car tires) to microgram quantities of
uorescent quantum dots (markers in biological imaging) which
can eventually end up in wastewater being fed to the wastewater
treatment plants.
4. Pertinence of nanoparticles in wastewater and wastewater

sludge
Water desalination, wastewater reuse and water disinfection
have been the principal segments of the markets with high growth
and prot potentials. Nanotechnology will bring about a complete
transformation in most of the technologies in the wastewater markets in the future (Environment Industry Survey, 2006).
Fig. 3. Typical wastewater treatment plant and possible fate (removal processes) of nanoparticles in each of the unit operations: (1) Collection system: use of products such
as, cosmetics, fragrances, pharmaceuticals, electronic systems and other products which comprise nanoparticles; (2) and (3) bar screen and grit removal: some nanoparticles
may be removed by the mechanism of adsorption onto large debris; (4) primary sedimentation system: via sedimentation and settling; (5) secondary treatment systems
(xed lm or suspended growth system): via settling, interaction with organic matter, microbial interactions; (6) secondary sedimentation: via sedimentation and
aggregation; (7) sludge thickener: concentration of nanoparticles; digester: via microbial interactions; organic matter interactions; sludge dewatering: via adsorption and
aggregation; landlls: via adsorption, leaching leading to groundwater and sub-surface water contamination; (8) disinfection process: via oxidant interactions; (9) release
into the receiving waters; and (10) advanced tertiary treatment: via oxidation and adsorption.
Table 4
Usage scenarios for emission of different products comprising nanomaterials into wastewater treatment plants.
Product type
Emission (g/pc/d)
Comments
References
Antiperspirant
Body lotion
Body wash
Cleaners
Deodorants
Face cream
Hair conditioner
Hair styling products
Lime deposit removers
Paint
Laundry detergents
Oral hygiene products
Perfume
Shampoo
Shaving foam
Soap
Skin care products
Softeners
Sunscreen
Window cleaners
0.35
1.2
0.32
0.3
0.08
1.64
0.47
0.10
0.11
0.090.36 ml/pc/yr
10.120.5
0.7
0.05
1.836.30
0.07
2.5
1.3
16.4
3.0
0.03
Based on 50% population use of the product at dose = 0.7 g/d

20% population use of the product at dose = 6.0 g/d
Home chemical usage survey in Denmark
20% population use of the product at dose = 8.2 g/d
Data on usage in the UK and release of 14% during cleaning
Data for USA, Sweden, Denmark, Finland and Norway
Survey of home chemical usage in Denmark
Dose = 0.5 g/d and 10% of population use product
Data for Sweden and Denmark
Data for Sweden
Date based on use in Europe
Dose = 30 g/d and 10% of population use product
Loretz et al., 2005, 2006

Eriksson et al., 2003
European Commission, 2004
Eriksson et al., 2002, 2003
pc refers to per capita.
It is a well-known fact that the particles in wastewater play an

important role in all kinds of water quality and treatment issues. In
addition to their smaller particle size, another factor that could
complicate the fate of nanoparticles in wastewater reclamation is
the functionalization of these particles for several applications (Savage and Diallo, 2005). Functionalization is the process by which
organic/surfactant molecules are attached to the nanoparticles to
keep them in dispersed state (Guo et al., 2006). As a result, nanoparticles may behave very differently than the conventional, dissolved contaminants as well as micron sized suspended particles
during wastewater treatment.
Meanwhile, whatever ends in wastewater is bound to nally
reach the wastewater sludge, more so through the agglomeration
and/or aggregation and settling mechanisms (Fig. 3) as discussed
later. Besides, wastewater sludge contamination by nanoparticles
is a completely neglected domain. Finally, the wastewater sludge
is spread on agricultural elds as biosolids raising issues on the potential leachability of nanoparticles into groundwater and sub-surface waters. In actuality, the amount of nanoparticles reaching soil
and natural waters depends on the fraction of wastewater that is
effectively treated. In the subsequent sections, we track the pathway of the nanoparticles during various unit operations of wastewater treatment plants. The mechanisms operating in a typical
wastewater treatment plant unit operation are illustrated in Fig. 4.
4.1. Preliminary treatment bar screens and grit removal
The predominant processes that will dictate the fate of nanoparticles will be sorption to the debris and other large particles
leading to their removal. However, it is possible that the majority
of nanoparticles may nd their way through wastewater to the primary treatment process.
4.1.1. Primary treatment
Primary settling process is a solidliquid separation process intended for removal of suspended, micron sized or larger inorganic
particles. Under laminar ow conditions, particle settling in sedimentation tank can be expressed by the Stokes Equation:
2
V s g=18l qs q d
where Vs = settling velocity; g = acceleration due to gravity;

qs = mass density of the particle; q = mass density of water;
Fig. 4. Hypothetical representation of mechanisms operating in a typical wastewater treatment plant process step (different mechanisms show further concentration into wastewater sludge).
511
d = diameter of the particle (Crank, 1975). The gravitational force

on a particle is a function of mass and hence, particle size and density. Likewise, buoyancy is a function of particle volume (size) and
the density of the liquid media (Bird et al., 1960). Drag is a function
of particle size, uid viscosity, and particle velocity.
As indicated in the Stokes Equation, settling velocity of particles is an exponential function of particle size. Accordingly, settling
velocity of nanoparticles will be several orders of magnitude
slower and hence, settling time will be of the orders of magnitude
higher than micron/submicron sized particles of the same material.
Hence, without the addition of coagulants and occulants to enhance the mean particle size, or without the adsorption of nanoparticles to large inorganic particles, nanoparticles are unlikely to
be removed in the primary sedimentation tanks.
However, most of the primary treatment processes comprise
extensive use of coagulants (AWWA, 2000) which may lead to
the adsorption of these nanoparticles and their further settling in
wastewater sludge. The nanoparticles may be further subjected
to numerous possible mechanisms in the wastewater sludge as
illustrated in Fig. 5.
In contrast to the soluble chemicals, particles can settle, diffuse,
and aggregate differentially according to their size, density, and
surface physical chemistry. The rate of gravitational settling is signicantly different across particle sizes and densities, although the
settling velocities of 100-nm particles and smaller particles can be
quite low. In the case of nanoparticles, the gravitational effect is
negligible and might it become signicant only when they are attached to other colloidal particles present in wastewater. Binding
to colloidal particles and/other microparticles can also alter the
hydrodynamic diameter of nanoparticles, with corresponding
changes in particle density/buoyancy (Tirado-Miranda et al.,
2003) and consequently settling rates. In fact, shape inuences
gravitational settling through effects on drag and buoyancy.
Though nanoparticles have many shapes, fractal agglomerates,
cubes, and rods, for instance, most of them can be adequately represented as spheres for the purpose of calculating gravitational settling rates. As a very general rule, particles with aspect ratios
greater than 2, carbon nanotubes, for example, cannot be represented as spheres for settling calculations (Swaminatan et al.,
2006), and alternative strategies should be used (Herzhaft and
Guazzelli, 1999). Nevertheless, for convenience, nanoparticles can
adsorb and agglomerate/conjugate with other particles present in
wastewater leading to gravitational settling as discussed earlier.
Limbach et al. (2008) performed a study on a model nanoparticle,
cerium oxide compound in a model wastewater treatment plant
and found that majority of the nanoparticles could be captured
through adhesion to clearing sludge, a signicant fraction of the
engineered nanoparticles escaped the wastewater plants clearing
system, and up to 6 wt% of cerium oxide was found in the efuent
stream. A detailed investigation on the agglomeration of oxide
Fig. 5. Probable mechanisms of nanoparticle accumulation/degradation in wastewater sludge.
512
nanoparticles in wastewater streams revealed a high stabilization

of the particles against clearance (adsorption on the bacteria from
the sludge). Hence, there are strong chances of their accumulation
into sludge and easy passage into the downstream processes.
Agglomeration involves the adherence of single or cluster of
particles into larger masses due to attractive forces or chemical
or mechanical binding (Maeakin, 1988). Irreversible agglomerates
of primary particles are called hard aggregates. Examples of this
type of agglomeration can be seen in electron micrographs of a
number of metal oxides (Limbach et al., 2005), C60 fullerenes
(Fortner et al., 2005), and carbon nanotubes (Lisunova et al.,
2006). Some nanoparticles have been manufactured as single particles; example, amorphous silica and polystyrene beads. Eventually, these particles can interact with each other to form soft
(reversible) agglomerates if there is a net attractive pair potential.
Many nanoparticles are in some degree of agglomeration in both
dry or solution forms (in this case, in the solution with different
type of ions in wastewater). Efcient aggregation and proper settling of ocs is important for the generation of good-quality efuent in the activated sludge process (Malik et al., 2003). The same
mechanism is going to hold good for the nanoparticles which can
form aggregates in the wastewater sludge. This fact was supported
by physical agglomeration of nanoparticles (on sludge bacteria),
adhesion of sludge to gas bubbles, and occasional transfer of sludge
into the aeration unit as reported in a recent model wastewater
treatment facility study (Limbach et al., 2008).
Agglomeration shifts the size class distribution of particles from
its initial state to one with a larger mean and in some cases, greater
dispersion of particle size distribution. Agglomerates have a higher
mass and volume than the individual particles they are composed
of and have correspondingly higher gravitational and buoyant
forces acting on them. Drag is also increased due to the higher volume and non-spherical shape. Agglomerates are not solid particles
due to spaces between individual packed particles (Sterling et al.,
2005) and therefore have a lower density and surface area:mass ratio than the primary particles (Johnson et al., 1996). The net effect
is that the settling rates for agglomerates are generally higher than
the smaller primary particles (primary reason for settling in primary sludge), but may be higher or lower than a comparably sized
single particle depending on the agglomerate shape and packing
density.
Several factors inuence the rate and extent of agglomeration:
(a) particle concentration affects the rate and degree of agglomeration via particle-to-particle interactions; (b) zeta potential; (c)
shape, and (d) hydrophobicity/hydrophilicity can also impact
agglomeration rates by inuencing repulsive or attractive (adhesive) properties. Fluid characteristics (van Oss et al., 1978) and
the extent and method of mixing also affect agglomeration (Limbach et al., 2005). The presence of polyelectrolytes on the particles
(which is the case in primary treatment process due to addition of
coagulants) can create a steric repulsive force and reduce the net
attractive interactions between particles, altering the agglomeration state. Microocculation (perikinetic occulation) will dominate in governing the aggregation of nanoparticles brought about
by the random thermal motion of uid molecules (Brownian motion). Microocculation has signicant inuence on transport of
particles that are in the size range from 0.001 to 1 lm. Moreover,
a suspension is a dispersion of solid particles in a liquid and nanoparticles will form a colloidal suspension. In the suspension of
large particles, for example 10 lm or larger, only hydrodynamic
interactions dominate the suspension ow properties and particle
packing behavior. However, in colloidal suspensions comprising
nanoparticles, inter-particle as well as hydrodynamic interactions
play a key role in determining the ow and particle packing properties. Aggregation phenomenon is also affected by the presence of
different ions in the solution (wastewaters have plenty of them, in
primary treatment, further aided by the commonly used coagulants, such as alum Fe3O4 that are added). Nanoparticles are likely
to undergo fast diffusive aggregation at higher ionic concentrations. In fact, fullerene nanoparticles have been reported to form
bigger aggregate structures under high salt conditions, eventually
settling out from the bulk phase of aquatic systems (Chen and
Elimelech, 2006).
The ionic strength of environmental systems may vary considerably, and this will also affect particle aggregation and thus transport. While aggregation of nanoparticles occurs over a wide range
of conditions, the aggregates are mobile (Park et al., 2004). This
must be taken into consideration for designing nanoparticle-based
environmental remediation systems, analyzing life cycles of nanoparticles used in commercial products, and determining potential
exposure to nanoparticles for health and impact studies from
wastewater and wastewater sludge. Transport distances may be
large enough for particles to cross redox zones, to move to regions
of different solution chemistry or surface charge, and to cross traditional barriers designed for contaminant removal. This scenario
may be prevalent in wastewater treatment plants while traversing
from one unit operation to another.
Hence, the particle size and concentration dependence of
agglomeration would alter the relationships between particle size,
concentration, and settling for agglomerating nanoparticles. The
aggregation and adsorption state of nanoparticles imposes questions on whether the nanoparticles will be truly mobile in the
wastewater environment leading to further contamination of other
environmental compartments. Likewise, other important particle
characteristics, such as zeta potential and mean hydrodynamic
diameter, which can directly or indirectly affect particle settling
should be a subject of extensive investigation in order to determine
the fate of nanoparticles in wastewater treatment processes. The
analytical methods have to be developed and strengthened in this
regard. The analysis will become more complicated when specicity of the nanoparticle has to be evaluated.
4.2. Secondary treatment process
4.2.1. Role of physical interactions
The secondary treatment processes comprise xed lm and suspended growth systems and corresponding secondary sedimentation systems. Both are aerobic systems involving entrainment of
air for microbial degradation of the organic matter. The secondary
treatment process environment is populated by microorganisms
where there is a possibility that the nanoparticles will adhere to
microbial cell surfaces or microbe-associated extracellular polymeric substances. Such a lm formation can have vital effects on
metabolic activity, for example, communication may be restricted
between the cell and its surrounding environment (quorum sensing). In fact, when polyelectrolyte-neutral block copolymers of
nanoparticles are mixed in solutions with oppositely charged species (e.g. surfactant micelles, macromolecules, proteins, etc.), there
is the formation of stable supermicellar aggregates that are a combination of both components (Jeong et al., 2003; Castelnovo, 2003;
Berret et al., 2004; Burgh et al., 2004; Berret and Oberdisse, 2004).
Furthermore, the xed lm systems might be clogged by the
presence of nanoparticles which may occupy active sites in the
xed membrane. It is possible that in clogging conditions which
may occur due to presence of these nanoparticles during transport
in xed lm systems, nanoparticle aggregates may act differently
than the solid particles. As the pores become clogged, the shear
forces due to uid ow would increase. The solid particles will
not be subject to breakage due to the shear forces, nanoparticle
aggregates may break apart, and re-entrainment may be greater
than for solid particles as was observed in literature in the case of
clay nano-composites (Oh et al., 2006). Furthermore, nanoparticle
aggregates may be subject to shear forces that may break up aggregates and reform them with other nanoparticles or nanoparticle
aggregates, an aspect that is not accounted for in current literature.
In addition, the shear forces required for nanoparticle disaggregation are generally not known and which will also inuence their
transport during secondary treatment.
4.2.2. Interaction with microorganisms
Another major interaction that the nanoparticles will experience during secondary treatment process is the interaction with
the microorganisms present. The processes, media properties,
and characteristics of particles that propel transport of nanoparticles to microorganisms comprise: diffusion, gravitational settling,
and agglomeration. Agglomeration and gravitational settling have
been already discussed in greater details. Hence, diffusion will be
explored in further details. Diffusion is the spontaneous, passive
movement of particles from high chemical potential to low chemical potential. There is no net transport by diffusion in systems at
equilibrium (Kikuo et al., 2006). Particles in microbial systems
are not necessarily in equilibrium. Particles adhere to microorganisms or are taken up by microorganisms, creating a concentration
gradient in the unstirred layer immediately above the microbial
cells. This gradient drives diffusional transport of particles. Rates
of diffusional transport are a function of particle size and the viscosity of the media (in this case, wastewater or wastewater
sludge). Smaller particles diffuse more rapidly than the large particles which will be the likely fate of nanoparticles. However, normally other media and particle characteristics (for instance,
charge and surface chemistry) do not affect diffusional transport
to a great extent. Diffusional transport can be estimated from the
diffusion coefcient (D, cm2/s) as given in Eq. (2):
RT
N6pld
where R = gas constant (8.314 J/K/mol), T = temperature (K),

N = Avogadros number, l = solution viscosity (kg/m/s), and d = particle diameter (m). Additionally, D is an inverse function of particle
size and is not a function of particle density (Einstein, 1905; Bergqvist et al., 1987). As the diffusion coefcient is inversely related to
particle size, delivery by diffusional transport is less important for
larger particles (above 100 nm); the time for a 1000-nm particle
to diffuse 1 cm is 3 years compared with only 1 day for 1-nm particles. Larger particles will be transported principally by gravitational settling, thus making diffusion a principal transport
phenomenon in secondary treatment.
No systematic studies have been performed to date to evaluate:
(i) removal of nanoparticles in secondary treatment processes, and
more so, (ii) impact of nanoparticles to the biomass. Only a few isolated studies are found on the subject which lead to some cohesive
conclusions. Zero-valent iron nanoparticles which nd wide application in removal of various pollutants in wastewater treatment
plants was found to have a strong bactericidal effect under de-aerated conditions (Lee et al., 2008a). On the contrary, air saturation
required much higher nano-Fe0 doses due to the corrosion and surface oxidation of nano-Fe0 by dissolved oxygen. Hence, these nanoparticles will undergo inactivation in the secondary treatment
processes and if escaped can cause inhibition downstream during
anaerobic digestion of wastewater sludge. Ivanov et al. (2004) evaluated retention of nano/micro latex beads (0.1, 0.6 and 4.2 lm)
and cells of Escherichia coli by microbial self-aggregated granules
in wastewater treatment plants. Microbial granules are spherical
biolm structures where microbes are attached to each other and
embedded in an extracellular matrix (Ivanov et al., 2004). Approximately 10% of 0.1 and 0.6 lm particles were removed by the biolm after 60 min of incubation. Furthermore, these particles
513
penetrated only to the top 250300 lm from the edge of the granule. Cells of E. coli on the other hand penetrated to approximately
800 lm of the biolm. Results from these studies indicated that
some nanoparticles can be removed by adsorption on activated
sludge. However, more studies are required to evaluate the extent
of nanoparticles adsorption to activated sludge, their removal in
secondary clariers as well as their fate during sludge digestion
processes. Some inferences in this context can be drawn from aseptic culture studies.
Lyon et al. (2005) and Fortner et al. (2005) evaluated the toxicity
of nanoscale carbon fullerene (nano-C60) to two facultative nitrate
reducing soil bacteria, E. coli (gram negative) and Bacillus subtilis
(gram positive). Nano-C60 is unique type of carbon nanoparticles
that are candidates for a variety of applications including drug delivery and energy conversion (Tufenkji and Elimelech, 2004). NanoC60, at 0.4 mg/l concentration, inhibited the growth of both the
microorganisms when grown in a basic media. Furthermore, when
4 mg/l of nano-C60 were added to these bacterial cells during their
log growth phase, their respiration rate signicantly slowed down.
Although these studies were performed using soil microorganisms,
results suggested that nanoparticles have the potential to inhibit
activated sludge process during water reclamation. Likewise, a study
carried out by An et al. (2007) demonstrated that the growth of
microorganisms was signicantly hindered by the silver nanoparticle coating. The potential for nanosilver to adversely affect benecial
bacteria in the environment, especially in soil and water is of particular concern. In fact, nanosilver nds use in the lining of refrigerators
and washing machines which can provide an active source for contamination. There is also a risk that the use of silver nanoparticles
(nanosilver) will lead to the development of antibiotic resistance
among harmful bacteria (Silver, 2003; Press release, 2006; Samsung
Silver Nano Health System, 2007). This would then require the separation of nanosilver from efuent during the sewage treatment process because of the danger that nanosilver would adversely affect
benecial bacteria in general and soil bacteria in particular (digested
sludge is marketed as an agricultural fertilizer) (Oberdrster et al.,
2005). Additionally, unextracted nanosilver could pollute the sea,
rivers and lakes, poisoning a variety of water organisms. This in turn
will greatly increase silver concentrations in treatment-plant discharges, leading to adverse effects, such as bioaccumulation in sh
and killing of aquatic life (Tang et al., 2004; Lubick, 2008). Furthermore, there is a possibility that nanoparticles and persistent organic
pollutants and other hazardous metals may form associations and
spread together, thereby amplifying their toxicity. Fullerene when
photosensitized in the disinfection processes of a typical wastewater
treatment plant has also been found to enhance viral inactivation
rates through the generation of superoxide and singlet oxygen
(Badireddy et al., 2007). A study in which the researchers dosed
the high concentration of 50,000 mg of C60 to 1 kg of sludge did
not affect the microbes chosen in the three domains of a genetic treebacteria, archaea and eukaryotes (Nyberg et al., 2008). Activity was
assessed by monitoring production of CO2 and CH4. Findings suggested that C60 fullerenes had no signicant effect on the anaerobic
community over an exposure period of a few months. However, the
slow growing nitrifying bacteria community is greatly affected by
nanoparticles. Size-dependent inhibition by Ag nanoparticles and
evaluation of the relationship between the inhibition and reactive
oxygen species demonstrated toxicity (Choi and Hu, 2008), thus
questioning their release into the wastewater streams. Furthermore,
electron micrographs of wastewater microbial community illustrated attachment of Ag nanoparticles to the microbial cells, probably causing cell wall pitting (Choi et al., 2008). The results suggested
that nitrifying bacteria were especially susceptible to inhibition by
Ag nanoparticles, and the accumulation of Ag nanoparticles could
have detrimental effects on the microorganisms in wastewater
treatment.
514
However, research is incomplete on the effects of nanoparticles

on other phyla such as, invertebrates and vertebrates from terrestrial and aquatic habitats. Since nanoparticles from both domestic
and industrial products will be released into the environment, e.g.
wastewater, it is essential to investigate the impact on such species
and further downstream on the ecosystem.
In fact, microorganisms and nanoparticles can develop symbiotic or similar synergistic relationships under specic environmental conditions. Microorganisms also have the potential to be
inuential catalytic agents. They can alter the oxidation state of
numerous elements (NSF, 2004). They can promote the removal
of specic molecules containing nanoparticles. Microorganisms
can also catalyze reactions that can lead to nanoparticle aggregation or molecule conjugation aiding in the removal. Thus, on one
hand, the nanoparticles have an adverse impact on the microbial
action and on the other hand, they synergize with microorganisms
to assist in auto-aggregation and nally removal. Similar types of
mechanisms are also possible in wastewater sludge which is a
warehouse of diverse microbial systems and may result in numerous mechanisms complexation, aggregation, among others
(Fig. 5).
In a typical wastewater treatment process, the nanoparticles
can adsorb to other nanoparticles and or macro and micropollutants leading to agglomerates which can form complexes (stable
or unstable) with extracellular polymeric substances resulting in
increased or decreased reactivity as demonstrated in Fig. 4. Biological uptake is a potential possibility for the microbial biomass present in the secondary treatment process, resulting in either
inhibition of the process or enhanced sorption/transformation of
the nanoparticles. The nanoparticles form aggregates which will
either deposit in the wastewater sludge and depending on the process conditions can undergo desorption and or complexation/ionization. This is a grave concern to any wastewater treatment facility
as biological treatment is the backbone of the facility, and without
it signicant reduction in contaminant loads would not be achievable. Presence of microorganisms in secondary treatment processes and eventual release of microbial exudates, such as
polysaccharides, among others may fuel the possibility of biodegradation of these nanoparticles.
4.2.3. Biodegradation processes
Biodegradation of nanoparticles may result in their breakdown
as typically seen in biodegradation of organic molecules, or may result in changes in the physical structure or surface characteristics
of the material. The potential and possible mechanisms of biodegradation of nanosized particles have just begun to be investigated.
As is the case for other fate processes, potential for biodegradation
will strongly depend on the physical and chemical nature of the
particle. Nanomaterials are composed of inherently non-biodegradable inorganic chemicals, such as ceramics, metals and metal
oxides, and are not expected to biodegrade. However, a recent preliminary study found that C60 and C70 fullerenes were taken up by
wood decay fungi after 12 weeks, suggesting that fullerene carbon
had been metabolized (Filley et al., 2005). For other nanomaterials,
biodegradability may be integral to the materials design and function. This is the case for some biodegradable polymers being investigated for use in drug transport (Madan et al., 1997; Brzoska et al.,
2004), for which biodegradability is mostly a function of chemical
structure and not particle size.
Biodegradability in waste treatment and the environment may
be inuenced by a variety of factors. Recent laboratory studies on
C60 fullerenes have indicated the development of stable colloid
structures in water that demonstrate toxicity to bacteria under
aerobic and anaerobic conditions (CBEN, 2005; Fortner et al.,
2005). Further studies are needed to determine whether fullerenes
may be toxic to microorganisms under environmental conditions.
One must also consider the potential of photoreactions and other

abiotic processes to alter the bioavailability and thus biodegradation rates of nanoparticles. In summary, not enough is known to
enable precise predictions on the biodegradation of nanomaterials
in the wastewater environment and further testing and research
are needed. A clear focus and comprehensive studies in the same
context might throw light on some of the unanswered issues.
4.2.4. Interaction with other pollutants
Nanoparticles such as, C60 have unique properties compared to
larger particles, and so they may have a very different effect on the
toxicity and availability of pollutants. Researchers from the Technical University of Denmark and the University of Copenhagen, Denmark tested the effect of four common pollutant chemicals:
atrazine, methyl parathion, pentachlorophenol and phenanthrene
on green algae and freshwater crustaceans (Baun et al., 2007). They
found that the presence of C60 nanoparticles affected the availability of the toxic chemicals to the organisms. C60 increased the toxicity of phenanthrene to algae at lower concentrations, for
instance, but decreased the toxicity against crustaceans. Likewise,
C60 made pentachlorophenol less toxic to both algae and crustaceans. C60 had little effect on the toxicity of the other two pollutants tested. Nanoparticles also affected the rate and quantity of
the pollutant taken in by the organisms. Clumps of C60 itself also
got stuck to the crustacean bodies and inside their digestive systems. Nevertheless, microorganisms and the extracellular material
associated with them are thought to play key roles in determining
the nanoparticle chemical speciation and its mobility in the environment (Kemner et al., 2004). This study is the rst of its kind
to demonstrate the inuence of C60-aggregates on aquatic toxicity
and bioaccumulation of other environmentally relevant
contaminants.
Hence, nanopollution in wastewater treatment plants must take
into account not just the toxicity of the particles themselves, but
also the possible interaction with other environmental contaminants. Moreover, further research into the effect of nanoparticles
different phases (in particular their behavior in wastewater as they
form suspensions or clumps of molecules known as aggregates) is
also relevant for their potential toxicity in the wastewater treatment plants and further the aquatic environment.
Colloids are known to control to a large extent, the transport of
pollutants in various environmental compartments. For example,
the colloidal pumping model (Honeyman and Santschi, 1992) can
give a clear explanation for the fate of pollutants through the environment: pollutants are hypothesized to bind preferentially to
small colloids which eventually aggregate into particles that are
large enough to settle. In groundwater and other porous media,
colloid-facilitated transport may be important in increasing distances travelled by pollutants and pathogens with respect to those
predicted for non-colloid bound components. The same hypothesis
can be extended to wastewater treatment plants when they pass
from one unit operation to other experiencing different hydrodynamic regimes as they form colloidal suspensions.
Nanoparticles of CeO2 (a strong oxidant), have recently been
shown to both decarboxylate and polymerize some small organic
molecules (Cervini-Silva et al., 2005). The environmental release
of CeO2 into the wastewater treatment plants may therefore potentially impact carbon chemistry and microbial interactions. Likewise, nanoparticulate oxides, such as TiO2, used to degrade
pollutants and as a disinfectant (Serpone and Khairutdinov,
1997; Kuhn et al., 2003; Rincon and Pulgarin, 2003), may have
the potential to induce other chemical transformations and impact
photochemical reactions in the gaseous phase of wastewater treatment plants which needs to be investigated.
The main models for understanding the uptake and bioavailability of trace metals by organisms are the equilibrium-based free
ion activity and biotic ligand models (Campbell, 1995; Paquin

et al., 2002; Slaveykova and Wilkinson, 2005). While hydrophobic
organic compounds (Galle et al., 2005) uptake is often reduced in
the presence of colloids, the general mechanisms upon which this
inhibition is based are unclear. A reduction in the diffusive mass
transport from the solution to microbial cell surface (the larger colloids are effectively prevented from having access to the microbial
cell because of slow diffusion) and a reduced chemical ability of the
colloidpollutant complex (as compared to the free metal or
inorganic complexes) may inuence bio-uptake, if these processes
become rate-limiting (Wilkinson and Bufe, 2004; Li et al., 2007b).
This can also affect the microbial removal of nanoparticles in
wastewater treatment processes.
The binding of nanoparticles to organic matter, metals, and
other contaminants could also have other undesirable consequences. For example, nanoparticle concentration in wastewater
sludge is also a possibility. Sludge is the result of accumulation
of solids removed during clarication. If nanoparticles were bound
with the solids, they would presumably be settled out and concentrated in the sludge during clarication.
In the other steps of wastewater treatment plant namely, disinfection, anaerobic digestion, the same processes as discussed earlier will predominate. Thus, a clear understanding of the
upstream processes will lend a helping hand to understand the
respective downstream processes. Finally, when the digested
dewatered sludge will be sent to landlls and as biosolids for agricultural application, leachability of nanoparticles is a possibility.
Thus, the mechanisms that govern the transport and fate of nanoparticles in water and soil and interaction with plants will predominate as discussed henceforth.
5. Transport during land application and/or landlling of

wastewater sludge
5.1. Fate in soil
The fate of nanoparticles released to soil is likely to vary
depending upon the physical and chemical characteristics of the
nanoparticle. Nanoparticles released to soil can be strongly bound
rendering them immobile. On the other hand, nanoparticles are
small enough to t into smaller spaces between soil particles,
and might therefore travel further than larger the particles before
becoming trapped in the soil matrix. The strength of the sorption of
any intentionally produced nanoparticle to soil will be dependent
on its size, chemistry, applied particle surface treatment, and the
application conditions. Studies have demonstrated the differences
in mobility of a variety of insoluble nanosized materials in a porous
medium (Zhang, 2003; Lecoanet and Wiesner, 2004; Lecoanet
et al., 2004). Humic substances, common constituents of natural
particles, are known to photosensitize a variety of organic photoreactions on soil and other natural surfaces that are exposed to sunlight. Some organic compounds tend to sorb to soils mainly via
interactions with soil organic matter.
Many reports have shown a positive correlation between the
organic C content and the sorption potential (Chefetz et al., 2000;
Ahmad et al., 2001; Gunasekara and Xing, 2003). Therefore, soil organic matter is considered to signicantly affect the fate of organic
compounds in the environment. In addition to the amount of soil
organic matter, the sorption afnity, as well as the desorption potential of organic compounds have been reported to be controlled
by the nature and chemical properties of soil organic matter and
kinetics of entrapment of sorbate, in this case, nanoparticles.
Meanwhile, the soil organic matter is very similar to organic matter of sludge. Suspensions of aggregated C60 fullerenes, when applied to soil at varying concentrations showed that the microbial
515
biomass and respiration rate (an indication of the activity of soil

microorganisms) were unaffected by nanoparticle treatments
(Johansen et al., 2008). Soil protozoans, such as amoeba, were
slightly sensitive, but fast-growing bacteria decreased up to 4-fold
in number. Thus, interactions between microorganisms in the soil
ecosystem are very complicated and the impact of fullerenes on
fast-growing bacteria may affect the balance of these interactions
and in turn the overall health and function of the soil.
Generally, nanoparticles interact with microorganisms present
in soil and groundwater through passive and active mechanisms
that alter the chemical form and hence the groundwater transport
and soil retention characteristics of the nanoparticles. This will
ultimately affect the human exposure route and toxicity. In a
study, gold nanoparticles functionalized with citrate were studied
for their mechanism of interaction with the soil microorganisms,
Pseudomonas uorescens (aerobic) and Clostridium sp. (anaerobic).
Changes in the nanoparticle surface chemical functionality and
aggregation behavior in water were studied after exposure to
growing and resting bacterial cells (Fitts et al., 2006). Gold nanoparticle surface plasmon resonance indicated modication of the
citrate functionality and aggregation. Soft X-ray scanning transmission spectromicroscopy revealed that nanoparticles were attracted to the bacterial cell surface; nanoparticlecell
interactions were also studied by transmission electron microscopy. These batch studies can also explain interactions with biolms where nanoparticles can undergo redox reactions due to
the presence of three zones, namely, aerobic, anoxic and anaerobic.
Furthermore, this will give a clear understanding of the predominant mechanisms of biotransformation in order to predict fate
and transport of nanoparticles in the wastewater treatment plants.
Studies of nanoparticle transformations in eld situations are
further complicated by the presence of naturally occurring nanoparticles of similar molecular structures and size ranges. Iron oxides are one example (Kamat and Meisel, 2003; Manceau et al.,
2008). Such kind of sorption and further mobility is also a possibility with nanoparticles as reported recently for aluminum nanoparticles (Darlington et al., 2009). Many factors inuence the transport
of nanoparticles in the environment. Size, charge, and the agglomeration rate of nanoparticles in the transport medium are indicators of nanoparticle mobility in soil which is possible on land
application of wastewater sludge based biosolids.
5.2. Fate in water
Fate of nanomaterials in aqueous environments is controlled by
solubility or dispersability, interactions between the nanomaterial
and natural and anthropogenic chemicals in the system, and biological and abiotic processes. Waterborne nanoparticles generally
settle more slowly than the larger particles. However, due to their
high surface-area-to-mass ratios, nanosized particles have the potential to sorb to soil and sediment particles (Oberdrster et al.,
2005a). The sorbed nanoparticles can be more readily removed
from the water column. Some nanoparticles will be subject to biotic and abiotic degradation resulting in removal from the water
column. Complexation by natural organic materials, such as humcolloids can facilitate reactions that transform metals in anaerobic
sediments (Nurmi et al., 2005).
For example, researchers at Rice University have reported that
although C60 fullerene is initially insoluble in water, it spontaneously forms aqueous colloids containing nanocrystalline aggregates. Currently, processes that control transport and removal of
nanoparticles in water and wastewater are being studied to understand nanoparticle fate (Moore, 2006; Wiesner et al., 2006).
Likewise, when the wastewater sludge as biosolids, loaded
with these nanoparticles will be applied to agricultural soils, there
is a likelihood of leaching through soils, further entraining through
516
the aquifer and affecting plant growth. There are contradicting and
scarce reports on this subject which involve over- or under-estimated concentrations and hence, data.
5.3. Interactions with plants
Only a few studies are available on the effects of nanoparticles
on higher plants. The majority of the reported studies point to the
positive impacts of nanoparticles on plant growth with a few isolated studies pertaining to negative effect. Numerous studies have
demonstrated that TiO2 nanoparticles promoted photosynthesis
and nitrogen metabolism, and thus greatly improved growth of
spinach at a concentration as low as 20 mg/L (Hong et al.,
2005a,b; Yang et al., 2006; Zheng et al.,2005; Lei et al., 2005). It
was also pointed out that a mixture of nanoscale SiO2 (nanoSiO2) and TiO2 (nano-TiO2) could increase nitrate reductase in
soybean (Glycine max), enhanced its abilities of absorption and utilization of water and fertilizer, stimulated its antioxidant system,
and apparently hastened its germination and growth (Lu et al.,
2002). However, after investigating the phytotoxicity of nanoscale
alumina (nano-Al2O3) powders with or without phenanthrene
coating, Yang and Watts (2005) concluded that uncoated alumina
particles inhibited root elongation of corn, cucumber, soybean,
cabbage and carrot. This study triggered the claim that nanoparticles can exert a negative effect on plants (Murashov, 2006). But, the
authors did not identify dissolution of nano-Al2O3 in solution, and
thus, failed to clarify if the phytotoxicity was from nano-Al2O3 or
aluminum ion in the aqueous solution.
Another study by Lin and Xing (2007, 2008) investigated phytotoxicology of nanoparticles (multi-walled carbon nanotube, aluminum, alumina, zinc, and zinc oxide) on seed germination and root
growth of six higher plant species (radish, rape, ryegrass, lettuce,
corn, and cucumber). Seed germination was not affected except
for the inhibition of nanoscale zinc (nano-Zn) on ryegrass and zinc
oxide (nano-ZnO) on corn at 2000 mg/L. Inhibition on root growth
varied greatly among nanoparticles and plants. Similar study by
Canas et al. (2008) investigated the effects of functionalized and
non-functionalized single-walled carbon nanotubes on root elongation of six crop species (cabbage, carrot, cucumber, lettuce,
onion, and tomato). Non-functionalized carbon nanotubes inhibited root length more than functionalized nanotubes. Microscopy
images showed the presence of nanotube sheets on the root surfaces, but no visible uptake was observed. In another study, Cu
nanoparticles were toxic to Phaseolus radiatus (mung bean) and
Triticum aestivum (wheat) and also were bioavailable (Lee et al.,
2008b). A cupric ion released from Cu nanoparticles had negligible
effects in the concentration ranges of the present study, and the
apparent toxicity clearly resulted from Cu nanoparticles. Similar
results were reported with the application of silica, palladium, gold
and copper nanoparticles on a soil microbial community and the
germination of lettuce seeds (Shah and Belozerova, 2009).
At this juncture, two schools of thought on positive and negative impacts of nanoparticles on plants are evident. Thus, no concrete conclusion can be drawn with respect to the nanoparticles
loaded in biosolids applied potentially to these soils and it represents a big lacuna in this eld. Moreover, studies reported so far
pertain to virgin nanoparticles whereas biosolids will be a mixture
of unchanged and transformed nanoparticles.
6. Future outlook
The discharge of nanoparticles from industrial waste or disposal
of such materials from commercial and/or domestic use will inevitably occur with increasing production and enter into wastewater
treatment facilities with unknown consequences. The fate of nano-
sized particles in wastewater treatment plants is not well investigated at this stage. However, it can be expected that bar screening
and other mechanical treatment methods will be ineffective at
removing any nanoparticles. Wastewater treatment operations
with the highest potential for removing nanoparticles from wastewater are the primary and secondary sedimentation tanks. Nevertheless, nanoparticle removal potential will rely on the specic
characteristics of the nanoparticles. The nanoparticle removal will
be facilitated through: (1) binding with organic matter which is
ultimately settled out; (2) natural aggregation with one another
thus improving settling; (3) binding with organic contaminants
and; (4) adherence to selective surfaces. The ability of either of
these processes to immobilize or modify the particles will depend
on the chemical and physical nature of the particle and the residence times in relevant compartments of the treatment plant.
Sorption, agglomeration and mobility of the nanoparticles will be
strongly dictated by pH. Settling of nanoparticles, however, could
be enhanced by entrapment in the much larger sludge ocs.
Sludges have the potential to contain high concentrations of
nanoparticles due to removal of water in a sludge thickening and
dewatering process. In addition, contaminants bound to these
nanoparticles (such as heavy metals) could also be present in dried
sludge. No studies were found so far that evaluated the potential
for nanoparticles in dried sludge to become airborne when the
material was agitated or transferred for disposal. This would also
be an occupational hazard issue. During biological treatment, some
nanoparticles have been found to inhibit or even prevent biological
activity. A reduction of biological activity by toxic nanoparticles
could decrease the contaminant removal effectiveness of the entire
facility failing efuent discharge limits. A total failure of the biological process could be experienced in the worst case. Furthermore,
nanoparticles could bind to piping, equipment, basin surfaces, be
difcult to remove, and require the complete shutdown and sanitization of the infrastructure affected before treatment could be
reinitiated. Unfortunately, limited research has been conducted
that would enable further conclusions on the fate of nanoparticles
on surfaces. Nanoparticle fate in sludge sent to landlls or incinerators must be evaluated. Major focus should be to understand
whether or not the nanoparticle is destroyed during sludge stabilization, incineration, and if nanoparticles could desorb and enter
landll leachate.
There is a need to evaluate whether or not nanoparticles exhibit
toxicity to wastewater and more specically wastewater sludge. It
still needs to be determined whether or not the bacteria in the activated sludge is protected signicantly enough by the extracellular
polymeric substances and whether or not there is toxicity in the
form of respiration inhibition when exposed to nanoparticles.
While the mechanisms of particle transport and the impact of particle size during wastewater treatment are well studied for micronsized pollutants, very little information is currently available on
the fate of nanoscale materials in treatment processes and relevant
studies are still at natal stage.
In general, particles at nanoscale behave differently than micron-suspended as well as totally dissolved chemicals in wastewater treatment processes. As a result: (i) increased release of
nanoparticles may affect the existing treatment processes, and/or
(ii) the nanoparticles may not be removed at the same efciency
as their conventional counterparts in the treatment process. In future, wastewater utilities as well as industries manufacturing
nanomaterials and those incorporating nanomaterials in their
products and equipment may have to include new treatment units
or alter their existing operations to remove nanoparticles from the
wastewater streams.
As the characteristic properties of nanomaterials are caused by
their high size surface to mass ratio, the aggregation behavior in
the environment is essential to study in detail. It could be
estimated that under certain conditions in the wastewater environment the particles tend to aggregate and therefore transport
in the environment is restricted e.g. sedimentation processes
(Degushi et al., 2001; Brant et al., 2005; Hyung et al., 2007). Parameters, such as pH, anions and cations (ion type and concentration)
and humic acids may inuence the surface properties and hence
chemical reaction of engineered nanoparticles. Thus, fate of nanoparticles in wastewater treatment plants is still not deciphered and
needs in particular, more detailed efforts for the fate in wastewater
sludge as it can have a cascading impact on the ecosystem. The disposition of nanoparticles following wastewater treatment will
determine their subsequent fate and transport pathways in two
ways via: (1) sewage sludge following land application and incineration and; (2) discharge water affecting aquatic organisms and
ecosystems.
7. Conclusions
The increasing use of nanoparticles in everyday products increases the potential for their release in water sources and wastewater streams. The release of nanoparticles into the wastewater
streams may have the following implications: (a) when present
in trace levels (lg/l and/or ng/l), based on toxicity study data, some
nanoparticles may potentially be added to the list of components
to be removed prior to water recharge/reuse applications and;
(b) when present in higher concentration (mg/l), the nanoparticles
may impact the performance of waste treatment processes by various mechanisms, including inhibition of microorganisms in secondary treatment process, increasing the turbidity, fouling of
membranes or affecting the efciency of disinfection processes.
No methodical studies have been performed till date to evaluate
the presence and removal of nanoparticles during various wastewater treatment processes and consequent presence in wastewater
sludge which is the ultimate sink. All cited studies were conducted
with well characterized, virgin materials. However, bacteria in
biological treatment processes are likely be exposed to weathered
nanoparticles that have undergone agglomeration and transformation, including loss or acquisition of coatings and impurities that
change surface chemistry, reactivity, bioavailability and toxicity
which needs to be addressed. There is a possibility that these nanoparticles agglomerate or even get adsorbed to the extracellular
polymers during primary and secondary treatment eventually ending up in wastewater sludge. Unfortunately, there will still be
many unanswered questions regarding nanoparticle fate and impact on wastewater facility and treatment operations. Another pertinent issue that needs to be addressed is whether the
nanoparticles in wastewater are a signicant environmental risk
when we are still tackling with other traditional pollutants, such
as heavy metals and polycyclic aromatic hydrocarbons.
Acknowledgements
The authors are sincerely thankful to the Natural Sciences and
Engineering Research Council of Canada (Discovery Grants A4984
and 355254, STP235071, Canada Research Chair) and INRS-ETE
for nancial support. The views or opinions expressed in this article are those of the authors and should not be construed as opinions of the US Environmental Protection Agency. We extend our
special thanks to Killam Foundation for granting Killam post-doctoral fellowship to Dr. Mausam Verma.
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Waste Management 30 (2010) 504520

Contents lists available at ScienceDirect

Engineered nanoparticles in wastewater and wastewater sludge Evidence

S.K. Brar et al. / Waste Management 30 (2010) 504520

gests that some nanoparticles escape from treatment plants and

Carbon nanotubes and

Nanolaminated or compositionally modulated

Silicon inversion layers in eld effect transistors

S.K. Brar et al. / Waste Management 30 (2010) 504520

Metals and alkaline

Antimicrobials, paints, coatings, medical use, food packaging

Cosmetics, paints, coatings

Substrate bound, but released with tyre wear

chondria (Foley et al., 2002). Lam et al. (2004) demonstrated that

Titanium dioxide (TiO2), silicon

Gram-positive Bacillus subtilis and Gramnegative Escherichia coli

The three photosensitive nanomaterials were

There is a need for caution during the use

US EPA, 2005; Adams et al.,

Silver (Ag), molybdenum (MoO3),

Cellular morphology, mitochondrial

Ag was highly toxic whereas, MoO3 moderately

Cellular response to nanosized particle

Hussain et al., 2005

Multi-walled carbon nanotube,

Seed germination and root growth of

Results are signicant in terms of use and

Lin and Xing, 2007

Fish brain tissue

Inhibition on root growth varied greatly among

Uncoated alumina particles

Corn, cucumber, soybean, cabbage and

Ultrane ambient particulate

Rat alveolar epithelial cells

Nano-C60, a fullerene aggregate

Classic engineered nanomaterial (nanoC60) contribute to the cytotoxicity

Sayes et al., 2005

Human dermal broblasts, human liver

Disruption of alveolar epithelial barrier

Possible and fugitive release of

Despite aiding in the absorption and

Wiwanitkit et al., 2007

Algae (Pseudokirchneriella subcapitata) and

On interaction with other organic compounds,

Water-soluble fullerene (nC60)

Daphnia magna and adult male fathead

Induction of lipid peroxidation in brain, in gill,

Spermatotoxicity of the gold nanoparticle

Yang and watts, 2005;

S.K. Brar et al. / Waste Management 30 (2010) 504520

Baun et al., 2007

Zhu et al., 2006

S.K. Brar et al. / Waste Management 30 (2010) 504520

3. Application of nanomaterials in decontamination of organic

S.K. Brar et al. / Waste Management 30 (2010) 504520

some of these nanoparticles are being deliberately loaded into the

small clusters are completely different from the better known

3.1. Physical regime of nanoparticles

3.2. Do nanoparticlenanoparticle interactions produce free

S.K. Brar et al. / Waste Management 30 (2010) 504520

To begin with, how do these nanoparticles nd their way into

4. Pertinence of nanoparticles in wastewater and wastewater

Based on 50% population use of the product at dose = 0.7 g/d