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Transformations of Nanomaterials in the Environment


Gregory V. Lowry,*,†,‡ Kelvin B. Gregory,†,‡ Simon C. Apte,§ and Jamie R. Lead∥,#

Center for Environmental Implications of Nanotechnology, Carnegie Mellon University, Pittsburgh, Pennsylvania, United States

Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, Pennsylvania, United States
§
Contaminant Chemistry and Ecotoxicology Program, CSIRO Land and Water, Locked Bag 2007, Kirrawee NSW 2232, Australia

School of Geography, Earth and Environmental Sciences, University of Birmingham, Birmingham, B15 2TT, U.K.
#
Department of Environmental Health Sciences, Arnold School of Public Health, University of South Carolina, Columbia, South
Carolina 29208
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

are engineered from more than one NM for optimized utility


(e.g., carbon nanotubes (CNTs) doped with quantum dots6).
These newly emergent materials that will soon enter manu-
facturing supply chains are unique and xenobiotic (e.g., metal
Downloaded via 152.58.37.151 on September 13, 2025 at 04:52:27 (UTC).

oxide NP-decorated graphene sheets7). The lack of a natural


analog for these new materials complicates the forecasting of
their fate, transport, reactivity and toxicity in environmental
systems. The uncertain effects resulting from the novel pro-
perties exhibited by NMs have given rise to concerns by citizens
and governments throughout the world, and a justified increase
in environmental health and safety (EHS) research aimed at
assessing the potential for NMs to harm the environment or
Increasing use of engineered nanomaterials with novel human health. An overall goal of these research activities is to
properties relative to their bulk counterparts has generated a correlate the properties of NMs to their behavior in the
need to define their behaviors and impacts in the environment. environment and their effects on living organisms.8
The high surface area to volume ratio of nanoparticles results in Assessing the environmental and human health implications
highly reactive and physiochemically dynamic materials in of nanomaterials requires an understanding of the potential
environmental media. Many transformations, e.g. reactions with exposure routes and toxicological effects from acute and
biomacromolecules, redox reactions, aggregation, and dissolu- chronic exposures. To date, the predominant focus of the
tion, may occur in both environmental and biological systems. global research endeavor has been defining the fate, transport,
These transformations and others will alter the fate, transport, and toxic properties of pristine or “as manufactured” nanoma-
and toxicity of nanomaterials. The nature and extent of these terials. However, the high surface to volume ratio and reactivity
transformations must be understood before significant progress of NMs makes them highly dynamic in environmental systems.
can be made toward understanding the environmental risks The resulting transformations of the NMs will affect their fate,


posed by these materials. transport, and toxic properties. For example, metallic silver NPs
will oxidize and may become sulfidized in the environment.9
INTRODUCTION Sulfidation of the particles changes their aggregation state,
The nanotechnology field continues to grow rapidly and surface chemistry, and charge, as well as their ability to release
the increasing use of engineered nanomaterials (NMs) in toxic Ag+ ions10 and therefore their persistence and toxicity.
commercial products translates into an increasing presence in Similarly, the interaction between NMs and humic substances
the biosphere. Engineered NMs are manufactured materials (HS) including natural organic matter (NOM) results in a
having at least one dimension in the nanoscale (ca. 1−100 nm) nanoscale coating of the NMs,11 analogous to protein coronas
dimension. Naturally occurring NMs are also ubiquitous in the in mammalian systems,12 that dramatically changes their aggregation,
environment, resulting from both natural processes and from deposition, and toxic properties.13,14
anthropogenic impacts (e.g., flocculation of nanometer-scale Because environmental systems are dynamic and stochastic,
metal oxides in acid mine drainage). The extremely small sizes the physicochemical changes that accompany engineered and
of both naturally occurring and engineered NMs results in a incidental coatings, as well as subsequent reactions in the
high percentage of surface atoms which can result in novel environment, greatly complicate the understanding of risks
properties and reactivity compared to a larger size material with associated with the release of NMs in the environment. We
the same chemical composition.1,2 Examples of such engineered currently lack sufficient knowledge of the types, rates, and
NMs include semiconductors like quantum dots which have extent of transformations expected for NMs in environmental
different optical and electrical properties depending on their and biological systems. By extension, we also fail to understand
size,3 and gold nanoparticles (NPs) that are typically inert but
become catalytic as their size is decreased to a few nanometers.4
Special Issue: Transformations of Nanoparticles in the Environment
NMs are becoming increasingly complex and include those
5
with coatings that target specific cells in the body or that Published: May 14, 2012

© 2012 American Chemical Society 6893 dx.doi.org/10.1021/es300839e | Environ. Sci. Technol. 2012, 46, 6893−6899
Environmental Science & Technology Feature

the impact of those transformations on the fate, transport, and Nanomaterials are commonly produced with an organic
toxicity of NMs. To correctly forecast the environmental and capping agent or stabilizer, often a small anion or polymer
human health risks associated with these materials, we must (Table 1). Transformations of the material can therefore affect
endeavor to broaden our knowledge of the transformations the core material, the capping agent, or both. For example,
of NMs. the simple coordination of ZnS nanoparticles (NPs) with water
The U.S. National Research Council has recently proposed a molecules can alter their crystalline phase and properties.19 The
new framework for nano EHS research.8 This committee recom- capping agent may be bioavailable and removed by bacteria.20
mended that research should focus on understanding “critical Indeed, the rate, extent, and type of transformations possible
elements of nanomaterial interactions”, needed for assessing expo- will depend on the properties of the initial NM, its coating, and
sure, hazards, and hence risks posed by engineered nanomaterials its surrounding chemical and biological environment. Impor-
(Figure 1). These critical elements include physical, chemical, and tantly, many transformations are slow or effectively irreversible
and cannot necessarily be predicted using thermodynamics.
Here, we briefly review what is known about chemical, physical,
and biologically mediated transformations of NMs in natural
systems and their effects on the resulting NM behavior. We
also discuss state-of-the-science knowledge and instrumentation
gaps preventing us from quantifying and predicting these
transformations in biological and environmental media.

■ NM TRANSFORMATIONS AND THEIR EFFECT ON


NM BEHAVIOR
Chemical Transformations (Figure 2a). Reduction and
oxidation are coupled processes in natural systems and involve
the transfer of electrons to and from chemical moieties. A
number of NMs may be composed of or contain constituents
Figure 1. Nanomaterial transformations are critical processes affecting that undergo reduction, oxidation, or both in aquatic and
NM interactions. Transformations include physical and chemical trans- terrestrial environments. These include elemental metal NMs
formations, biologically mediated transformations, and interactions such as silver21,22 and iron.23 Ceria NPs can contain both
with macromolecules and biomacromolecules. Adapted from ref 8. Ce(III) and Ce(IV) and subsequent sorption of macromole-
cules can alter the ratio of Ce(III)/Ce(IV) on the NP surface.24
biological transformations that ultimately influence NM persis- The sulfur and selenium in some metal sulfides and metal
tence, bioavailability/biouptake, reactivity, and toxicity. selenides, major components of quantum dots, are also
Oxidation and reduction (redox) reactions, dissolution, susceptible to oxidation that may release soluble toxic metal
sulfidation, aggregation, and adsorption of macromolecules ions such as Cd.2,25 In some cases, oxidation may result in the
and molecules/ions all readily occur in the environment and in accumulation of a relatively insoluble oxide surface coating on
biological systems. These transformations greatly impact NM the NP that passivates the surface and reduces subsequent
behavior. In some cases, these transformations may enhance oxidation, while also forming metal-oxide phases with a high
toxicity potential (e.g., chemical weathering of the shell of a capacity for binding ions from solution. In other cases, (e.g., Ag
Cd−Se quantum dot that releases toxic ions from the particle NPs), oxidation of Ag(0) to Ag(I) is required to dissolve and
core).15 In other cases, these transformations have been shown release bactericidal Ag+.22 Natural waters and aerated soils are
to decrease effects (e.g., adsorption of NOM decreased the predominantly oxidizing environments, while carbon-rich
short-term bactericidal effects of C60, Ag NPs, and Fe(0) sediments and groundwater may be depleted of oxygen and
NPs,13,14,16 but increased bioaccumulation17). Some transforma- result in NM reduction. In dynamic redox environments such
tions can potentially limit NM persistence in the environment as tidal zones one may well encounter cycling of NMs between
(e.g., dissolution of ZnO NPs).18 There is still a great deal of un- different redox states.
certainty about the role that transformations have on both Sunlight-catalyzed redox reactions (photooxidation and photo-
exposure and biological effects across the whole life cycle of NMs. reduction) may prove to be very important transformation

Table 1. Representative Nanomaterials and Capping Agents/Coatings

typical capping agents/coatings


nanomaterial inorganic and small organic molecules synthetic and organic macromolecules
zinc oxide 2-mercaptoethanol, triethoxycarprylsilane, triethanolamine, acetate polyvinylpyrrolidone (PVP), polysaccharides,
silver citrate, decanethiol, tannic acid, ethylenediaminetetraacetic acid (EDTA) polyethylene glycol (PEG), PVP, gum arabic
gold citrate, octanethiol, cetyltrimethyl ammonium bromide (CTAB), cysteine, biotin, bovine serum albumin (BSA), polypeptides
tannic acid
cerium oxide oleic acid PVP, poly(acrylic acid)-octyl amine
titanium dioxide oleic acid Poly(acrylic acid)
quantum dots (CdSe, Silica (inorganic), zinc sulfide (inorganic), citrate, mercaptopropionic acid PEG, aminodextran
CdS)
iron oxide dodecylamine, oleic acid BSA, poly(acrylic acid), poly(methacrylic acid), PEG
zerovalent iron (ZVI) Au, Pd, Pt, Ni carboxymethyl cellulose, xanthan gum, polypropylene
glycol

6894 dx.doi.org/10.1021/es300839e | Environ. Sci. Technol. 2012, 46, 6893−6899


Environmental Science & Technology Feature

Figure 2. (a) Representative chemical transformations of metal nanomaterials and the potential impacts on their behavior and effects in the
environment. AgNPs are used to exemplify the types of transformations that may occur. The magnitude of arrows approximately correlates with
potential for these processes to occur as determined from the limited data available on these processes. (b) Effects of physical transformations
including aggregation and heteroaggregation on the reactivity and transport of nanomaterials. The magnitude of arrows approximately correlates
with potential for these processes to occur as determined from the limited data available on these processes. (c) Biologically mediated
transformations of nanomaterials and their coatings, and the subsequent impact on fate, transport, and effects. Arrows do not indicate the relative
potential for these processes to occur due to the limited data currently available for that assessment. (d) Effects of nanomaterial interactions with
macromolecules such as proteins and natural organic matter. Adsorbed macromolecules can affect aggregation, nanoparticle-biointeractions,
biouptake, and fate, transport, and effects in the environment. Arrows do not indicate the relative potential for these processes to occur due to the
limited data currently available for that assessment.

processes affecting NM coatings, oxidation state, generation of highly reactive with sulfur-containing biomacromolecules and
reactive oxygen species (ROS), and persistence. The oxidation inorganic sulfur in sediments, soils, and air. Formation of a
and mineralization of fullerenes dispersed in water by natural relatively insoluble metal-sulfide shell on the particle surface
sunlight may attenuate carbon-based nanomaterials.26 Sunlight can alter the surface charge and induce aggregation.10 Deter-
exposure caused the degradation of gum arabic coatings on Ag mining the particle properties (e.g., particle size, capping agent,
NPs and induced aggregation and sedimentation from solution.27 etc.) and environmental conditions (redox state and availability
Many NMs will be innately photoactive (e.g., TiO2 and CNTs), of free sulfide) that affect their dissolution and/or sulfidation
potentially producing ROS when exposed to sunlight.28 Others rates are important for assessing their potential to release toxic
may be oxidized or reduced by sunlight, changing their redox metal cations, and their ultimate toxicity29 and persistence in
state, charge, and therefore potential for toxicity. the environment.30
Dissolution and sulfidation are important processes affecting Adsorption of macromolecules or organic and inorganic
NP surface properties, toxicity, and persistence. This is especi- ligands on NM surfaces can significantly affect their surface
ally true for NMs made from Class B soft metal cations (e.g., chemistry and resulting behavior in biological and environ-
Ag, Zn, and Cu) because they form partially soluble metal- mental systems. For example, adsorption of polymer coatings
oxides, and because they have a strong affinity for inorganic and on NPs generally decreases their attachment to silica surfaces,
organic sulfide ligands. Class B metal NMs commonly express suggesting greater mobility in the environment and potentially
toxicity through dissolution and release of toxic cations, such less effective removal in drinking water treatment.31 Adsorption
that persistence is reduced but toxicity is increased. Complete of biomacromolecules is a particularly important transformation
dissolution may allow prediction of their impact using existing and is treated separately below. Adsorption of organic ligands
models for metal speciation and effects. However, Class B or metal cations or oxo-anions can occur on either the surface
metals’ affinities for electron-dense sulfur molecules make them of the core NM or within the organic macromolecular coating
6895 dx.doi.org/10.1021/es300839e | Environ. Sci. Technol. 2012, 46, 6893−6899
Environmental Science & Technology Feature

of the particle. Organic ligands, such as those containing thiol Biologically mediated transformations of both the underlying
groups may affect NM dissolution, charge, and stability against NM core and the coatings are possible, and these trans-
aggregation.32,33 Organics present in the atmosphere can also formations can affect the behavior of the NMs including surface
condense onto airborne NMs, altering their surface chemistry.34 charge, aggregation state, and reactivity, which ultimately can
Understanding the effects of organic ligands and adsorbed affect transport, bioavailability, and toxicity. The oxidation and
cocontaminants on NM toxicity is needed to fully assess the carboxylation of CNTs by OH radicals produced from the
potential for harm. horseradish peroxidase enzyme has been demonstrated.40 This
Physical Transformations (Figure 2b). Aggregation of oxidation increases the surface charge of the CNTs and stability
NPs reduces the surface area to volume effects on NM against aggregation while decreasing hydrophobicity. Moreover,
reactivity. This increase in aggregate size in turn affects their this biological oxidation and surface functionalization may affect
transport in porous media, sedimentation, reactivity, uptake by the toxic potential of CNTs.41
organisms, and toxicity. Over time, aggregation of NPs into Biotransformation of polymer coatings used on many NMs
clusters is inevitable without engineered or incidental coatings for biomedical applications is also feasible. Covalently bound
to decrease aggregation. Aggregation may take on two forms: poly(ethylene glycol) (PEG) coatings on engineered NMs, for
homoaggregation between the same NMs, or heteroaggregation instance, were shown to be bioavailable to microorganisms
between a NM and another particle in the environment. In isolated from an urban stream.20 Moreover, the biotransforma-
most cases, the greater concentration of environmental particles tion of the PEG coating caused the NMs to aggregate.
compared to NMs will result in heteroaggregation. Where Biological transformations of NMs, especially carbon-based
aggregation occurs, the number concentration of NMs in the ones, and their organic coatings may ultimately act to attenuate
suspension decreases, with a concomitant increase in their their concentrations in the environment or to affect transport,
effective (aggregate) size. For example, 30−70 nm diameter but it remains to be seen if these processes occur at rates that
Fe(0) NPs rapidly aggregate in water to form micrometer- are high enough to be important. Perhaps the most critical
sized aggregates,35 greatly decreasing their mobility in the sub- biotransformation of NMs is adsorption of biomacromolecules
surface and likely pathways of exposure to sensitive receptors. on their surfaces as discussed next.
Heteroaggregation between NMs and comparatively larger Macromolecule NM Interactions (Figure 2d). There
particles (e.g., clay) could change NM behavior if the NM−clay are an endless number of biomacromolecules in living cells
heteroaggregates ultimately move more like a clay particle that (e.g., proteins) and in the environment (e.g., NOM, poly-
the NM.36 saccharides). Adsorption of these macromolecules can occur in
Aggregation can also decrease the “available” surface area of
all environments. On uptake by biological organisms, NMs may
the materials, thereby decreasing reactivity. However, the
be transformed through their interaction with biomacromolecules
decrease in specific surface area will depend on particle number,
which can coat and thereby transform their outer surfaces.42
size distribution, and the fractal dimensions of the aggregate.37
Adsorbed protein coatings, also known as protein coronas, form
Aggregation can therefore decrease toxicity when the toxic
in biological fluids for several classes of NMs.12,43,44 The
response is a result of a surface area-mediated reaction such as
coronas result from the adsorption of a wide range of proteins
ROS generation or dissolution. Aggregation may also serve to
increase the persistence of the NM if aggregation decreases the and are dynamic in nature, with the proteins capable of exchang-
rate of dissolution or degradation, albeit in a different location ing between free and bound forms. However, many proteins and
compared to the dispersed NPs. The size of a NP may also other macromolecules are effectively irreversibly adsorbed over
affect its bioavailability to organisms. When aggregates or relevant time scales,45,46 and therefore in part determine the
heteroaggregates become too large for direct transport across “identity” of the NM (e.g., size, electrophoretic mobility, and
the cell wall and/or membrane, uptake may be prevented. surface composition) and subsequent environmental behavior
Phagocytosis and similar mechanisms may also be affected. and biological response. The adsorbed proteins may also offer a
Conversely, heteroaggregation with soft biogenic particles way of entry for NMs into cells through the process of receptor-
might increase NM bioavailability (e.g., uptake by filter feeders mediated endocytosis.44 The presence of biomacromolecules can
who preferentially remove larger particles). Delineating the affect their dissolution rate, ROS production, and may determine
effects of aggregation on uptake and any subsequent toxicity the fate of the material in the organism (e.g., excretion vs accu-
will be challenging since it is a dynamic process, uptake will be mulation in specific organs). Therefore, the types of biomacro-
highly dependent on both the species examined and its aqueous molecules present on the surface can affect important processes
chemical environment and metabolic state, and because such as bioaccumulation and toxicity.
instruments for tracking NMs in situ or in vivo are lacking. Once discharged into the environment, uncoated or coated
Biologically Mediated Transformations (Figure 2c). NMs will be subjected to alterations through interactions with
Biological transformations of NMs are inevitable in living naturally occurring biomacromolecules or geomacromolecules
tissues (both intracellular and extracellular) and environmental including proteins, polysaccharides, and humic substances
media (e.g., soils). Redox reactions are fundamental to growth (HS). NOM concentrations are typically orders of magnitude
in all biological systems. These reactions take place in the higher in concentration than manufactured NMs and so are
cytoplasm, cell wall, cell membrane, and extracellularly via likely to substantially modify the properties and behaviors of
redox-labile enzymes and cytochromes or through ancillary the manufactured NMs. The observed interactions are
intracellular ROS production such as hydroxyl radicals or H2O2. analogous to the interactions with proteins and the formation
The redox reactions between bacteria and naturally occurring, of “protein coronas” in biological systems, which have been the
nanoscale iron oxide are well understood.38 Moreover, bacteria subject of more intensive research reaching similar conclusions;
such as Geobacter and Shewanella spp. were recently the behavior and impacts of NMs depends highly on the types
demonstrated to produce nanoscale silver particles by reduction and amounts of these biological and environmental compo-
of Ag+ from solution.39 nents attached to their surfaces.
6896 dx.doi.org/10.1021/es300839e | Environ. Sci. Technol. 2012, 46, 6893−6899
Environmental Science & Technology Feature

Most work to date on NM−NOM interactions has been because the arrangement on the surface to reach the final
performed using extracted humic substances (HS), which will conformation is slow. Third, NMs will likely undergo multiple
displace weakly bound synthetic capping agents on the particle transformations simultaneously (e.g., interaction with NOM
surface to form nanoscale coatings which can be either coherent and oxidation or reduction), or successive irreversible transfor-
(i.e., fully coating the NM surface) or noncoherent. They mations (e.g., irreversible adsorption of different proteins upon
can form relatively “flat” monolayers or more extended (thick) successive exposures to plasma and intercellular materials).53
monolayers or multilayers. The coherence and thickness Therefore, answering the question of how a specific NM will
depend on the particle properties and the conditions (e.g., behave in the environment requires information about the
pH and ionic strength) during interaction. NOM provides both environment properties and the history of the NM over time
charge and steric stabilization of NMs,11,47 although they may scales of interest. We will have to address this using a well-
also result in bridging flocculation,24 so their effects are com- planned (and likely multidimensional) matrix of representative
plex and can be difficult to predict. In addition, deagglomera- materials and media, as opposed to a case by case basis, because
tion may occur in the presence of NOM.48 For larger MW the large number of permutations of NMs and environmental
polymeric coatings that are strongly bound mixed polymer− systems makes the latter impossible in practice. Simplification
NOM layers may form on NMs, however, in some cases may be possible by measuring transformations in specific
interactions with NOM may be minimal.49,50 The conditions representative environments, i.e. environmental and biological
under which mixed layers form and the influence of those layers matrices, at both short times and long times to capture the end
on NM behavior has yet to be explored. member behaviors expected.
NOM coatings on NMs will affect the attachment to surfaces, There are many instruments available to measure the pro-
and therefore both homoaggregation and heteroaggregation perties of NMs such as chemical composition, size, and charge.
described previously. However, determining the interaction However, most of these techniques are generally not capable
between NMs and every type of environmental surface (various of measuring these properties in situ and in vivo or in
clay surfaces, iron oxides, quartz, etc.) is not feasible. The environmentally relevant concentrations and conditions.
problem may be simplified, however, if the NOM coatings on Equally importantly, methods are needed to better track the
the NM (and on the environmental surfaces) are relatively rate and extent of transformations of NMs under realistic
coherent. Then all surfaces would be expected to behave conditions, especially for those where multiple transformations
similarly and complex heteroaggregation phenomena may be occur. Method validation and development are required to take
treated as simpler homoaggregation processes, at least to a first this forward and greater collaboration between metrological
approximation. The influence of the underlying NM properties and analytical researchers with environmental scientists and
and the NOM−NM interactions on the resulting forces affect- environmental chemists is needed. In some cases, trans-
ing attachment must be determined to test this hypothesis. formations of NMs will occur over time scales of months or
In addition to changes in aggregation and disaggregation, years. Understanding these transformations completely will
interaction with NOM has been shown to reduce short-term require an ability to recover the NMs from environmental and
bacterial toxicity for fullerenes,14 Ag(0),13 and Fe(0),51 while biological matrices and measure the properties of these partially
increasing bioaccumulation in biofilms. 17 In all cases, transformed NMs, or to measure them in vivo/in situ. A
presumably the NOM had the effect of “masking” the NP recent NRC report provides more specific suggestions for tools
effect, either by directly coating the surface or by minimizing and instrumentation that are needed to advance nano EHS
dissolution. NOM have also been known to alter surface research.8
chemistry, for instance altering ceria NM oxidation state.24
Changing the redox state of the NM can affect its toxicity and
mechanisms of action as described above.
■ IMPLICATIONS OF NM TRANSFORMATIONS ON
NANO EHS RESEARCH

■ KNOWLEDGE GAPS AND MEASUREMENT


CHALLENGES
Transformations of NMs will readily occur in the environment
and in vivo, which greatly affects their properties, behavior, and
effects. However, most toxicity, fate, and transport studies to
Engineered NMs in natural systems are subject to a dynamic date have used relatively pristine materials, which will behave
physical and chemical environment that will drive the particles differently than the transformed ones. While the effects mea-
away from their pristine or “as manufactured” state, toward sured for relatively pristine materials may be representative of
largely unknown end points and products. Characterizing and human exposures occurring at manufacturing or processing
predicting environmental transformations can pose a tremen- sites where direct exposure to relatively pristine NMs is
dous challenge for several reasons. First, the types of trans- possible, environmental exposures to aquatic organisms and to
formations expected will depend on the solution conditions humans (e.g., via drinking water or food ingestion) will be to
(e.g., pH, redox state, organic matter content, types of serum transformed NMs so data regarding fate and effects of pristine
components present); even slight variations between systems NMs may not be particularly informative. The research
may lead to different behaviors. Second, many of the community instead needs to focus on understanding the
transformations are dynamic but not readily reversible and reactivity, fate, mobility, persistence, and effects of the “aged” or
therefore the history of the NM will affect its properties and transformed NMs where the “aging” process best represents the
state in the environment. For example, a Ag NP might be history of the NM prior to the exposure.
readily sulfidized in wastewater treatment plants to a Ag2S Environmental exposures to NMs are likely to be chronic and
NP.52 However, the resulting Ag2S NP is likely stable against at low concentration. Therefore, slow transformations of NMs
reoxidation so release of these particles to an oxic water column will need to be assessed to understand the ultimate fate and
might not necessarily result in the thermodynamically predicted distribution in the environment and potential for harmful
end member NP (e.g., AgCl). Similarly, adsorbed macro- effects. Some transformations, e.g. adsorption of biomacromo-
molecules are almost never at their final equilibrium state lecules or dissolution of metal NPs, are fundamental processes
6897 dx.doi.org/10.1021/es300839e | Environ. Sci. Technol. 2012, 46, 6893−6899
Environmental Science & Technology Feature

that will affect NM behavior both in the environment and in (3) Alivisatos, A. P. Semiconductor clusters, nanocrystals, and
vivo. Virtually nothing is presently known about the rates of quantum dots. Science 1996, 271, 933−937.
these transformations under relevant conditions. Determining (4) Haruta, M. Gold as a novel catalyst in the 21st century:
the potential for these fundamental processes to occur, and the Preparation, working mechanism and applications. Gold Bull. 2004, 37,
27−36.
rates of these processes, should be a research priority because
(5) Byrne, J. D.; Betancourt, T.; Brannon-Peppas, L. Active targeting
advances in this area will benefit multiple nano EHS research schemes for nanoparticle systems in cancer therapeutics. Adv. Drug
communities, e.g. fate and transport, toxicology, and sustain- Delivery Rev. 2008, 60, 1615−1626.
able/green nanotechnology. (6) Guldi, D. M.; Rahman, G. M. A.; Sgobba, V.; Kotov, N. A.;
Classifications of NMs are desirable for regulatory purposes. Bonifazi, D.; Prato, M. CNT-CdTe versatile donor-acceptor nano-
Because most NMs are highly reactive, and because those hybrids. J. Am. Chem. Soc. 2006, 128, 2315−2323.
transformations dramatically affect their fate and effects, it may (7) Wang, D. H.; Kou, R.; Choi, D.; Yang, Z. G.; Nie, Z. M.; Li, J.;
be possible to classify NMs, at least in part, by their expected Saraf, L. V.; Hu, D. H.; Zhang, J. G.; Graff, G. L.; Liu, J.; Pope, M. A.;
environmental transformations, although incorporating this Aksay, I. A. Ternary self-assembly of ordered metal oxide-graphene
into current legislation and regulatory practice will be nanocomposites for electrochemical energy storage. ACS Nano 2010,
challenging. Some NMs may require more than one 4, 1587−1595.
(8) NRC. A Research Strategy for Environmental, Health, and Safety
classification depending on the environment in which they
Aspects of Engineered Nanomaterials; The National Academies Press:
reside. Transformations can lead to materials that can be more Washington, DC, 2012.
heterogeneous than the parent NM, making characterization (9) Lowry, G. V.; Espinasse, B. P.; Appala, R.; Richardson, C.;
difficult. However, it is also possible that transformations may Reinsch, B. C.; Bryant, L. D.; Bone, A.; Deonarine, A.; Chae, S.;
decrease heterogeneity if ubiquitous transformations (e.g., Therezien, M.; Colman, B. P.; Hsu-Kim, H.; Bernhardt, E.; Matson, C.
coating with humic acids, NOM, or proteins, or sulfidation) W.; Wiesner, M. W. Long-term transformation and fate of
lead to NMs with behaviors that are less influenced by the NM manufactured Ag nanoparticles in a simulated large scale freshwater
core than by the coating. Transformations and the properties of emergent wetland. Environ. Sci. Technol. 2012, No. 10.1021/
the transformed NM will ultimately depend on the environ- es204608d.
ment that they enter, and on the order of the environments in (10) Levard, C.; Reinsch, B. C.; Michel, F. M.; Oumahi, C.; Lowry,
which they are exposed. This fact, and the uncertainty regarding G. V.; Brown, G. E. Sulfidation processes of PVP-coated silver
use and release scenarios, makes the determination of risk nanoparticles in aqueous solution: Impact on dissolution rate. Environ.
Sci. Technol. 2011, 45, 5260−5266.
challenging.


(11) Diegoli, S.; Manciulea, A. L.; Begum, S.; Jones, I. P.; Lead, J. R.;
Preece, J. A. Interaction between manufactured gold nanoparticles and
AUTHOR INFORMATION naturally occurring organic macromolecules. Sci. Total Environ. 2008,
Corresponding Author 402, 51−61.
*E-mail: [email protected]. (12) Cedervall, T.; Lynch, I.; Lindman, S.; Berggard, T.; Thulin, E.;
Nilsson, H.; Dawson, K. A.; Linse, S. Understanding the nanoparticle-
Notes protein corona using methods to quantify exchange rates and affinities
The authors declare no competing financial interest. of proteins for nanoparticles. Proc. Natl. Acad. Sci. U.S.A. 2007, 104,
2050−2055.
Biography (13) Fabrega, J.; Fawcett, S. R.; Renshaw, J. C.; Lead, J. R. Silver
nanoparticle impact on bacterial growth: Effect of pH, concentration,
Greg Lowry is a Professor of Environmental Engineering at Carnegie
and organic matter. Environ. Sci. Technol. 2009, 43, 7285−7290.
Mellon University in Pittsburgh, PA and Deputy Director of the Center
(14) Li, D.; Lyon, D. Y.; Li, Q.; Alvarez, P. J. J. Effect of soil sorption
for Environmental Implications of Nanotechnology (CEINT). Kelvin and aquatic natural organic matter on the antibacterial activity of a
Gregory is an Associate Professor of Environmental Engineering at fullerene water suspension. Environ. Toxicol. Chem. 2008, 27, 1888−
Carnegie Mellon University. Simon Apte leads the Contaminant 1894.
Chemistry and Ecotoxicology Program at CSIRO Land and Water, (15) Mahendra, S.; Zhu, H. G.; Colvin, V. L.; Alvarez, P. J. Quantum
Sydney Australia. Jamie Lead is Professor of Environmental Nanoscience dot weathering results in microbial toxicity. Environ. Sci. Technol. 2008,
at the University of Birmingham, UK, and Professor of Environmental 42, 9424−9430.
Nanoscience and Risk at the University of South Carolina, USA. (16) Tong, Z. H.; Bischoff, M.; Nies, L.; Applegate, B.; Turco, R. F.


Impact of fullerene (c-60) on a soil microbial community. Environ. Sci.
Technol. 2007, 41, 2985−2991.
ACKNOWLEDGMENTS (17) Fabrega, J.; Renshaw, J. C.; Lead, J. R. Interactions of silver
G.V.L. and K.B.G. were supported by the Center for nanoparticles with Pseudomonas putida biofilms. Environ. Sci. Technol.
Environmental Implications of Nanotechnology (funded by 2009, 43, 9004−9009.
the National Science Foundation and the U.S. Environmental (18) Bian, S. W.; Mudunkotuwa, I. A.; Rupasinghe, T.; Grassian, V.
Protection Agency under grant EF-0830093. J.R.L. acknowl- H. Aggregation and dissolution of 4 nm ZnO nanoparticles in aqueous
edges financial support from the Natural Environment Research environments: Influence of ph, ionic strength, size, and adsorption of
humic acid. Langmuir 2011, 27, 6059−6068.
Council (NERC FENAC and NE/H013148/1).


(19) Zhang, H. Z.; Gilbert, B.; Huang, F.; Banfield, J. F. Water-driven
structure transformation in nanoparticles at room temperature. Nature
REFERENCES 2003, 424, 1025−1029.
(1) Auffan, M.; Rose, J.; Bottero, J. Y.; Lowry, G. V.; Jolivet, J. P.; (20) Kirschling, T. L.; Golas, P. L.; Unrine, J. M.; Matyjaszewski, K.;
Wiesner, M. R. Towards a definition of inorganic nanoparticles from Gregory, K. B.; Lowry, G. V.; Tilton, R. D. Microbial bioavailability of
an environmental, health and safety perspective. Nat. Nanotechnol. covalently bound polymer coatings on model engineered nanomateri-
2009, 4, 634−641. als. Environ. Sci. Technol. 2011, 45, 5253−5259.
(2) Hochella, M. F.; Lower, S. K.; Maurice, P. A.; Penn, R. L.; Sahai, (21) Henglein, A. Colloidal silver nanoparticles: Photochemical
N.; Sparks, D. L.; Twining, B. S. Nanominerals, mineral nanoparticles, preparation and interaction with O2, CCl4, and some metal ions. Chem.
and earth systems. Science 2008, 319, 1631−1635. Mater. 1998, 10, 444−450.

6898 dx.doi.org/10.1021/es300839e | Environ. Sci. Technol. 2012, 46, 6893−6899


Environmental Science & Technology Feature

(22) Lok, C. N.; Ho, C. M.; Chen, R.; He, Q. Y.; Yu, W. Y.; Sun, H.; (42) Nel, A. E.; Madler, L.; Velegol, D.; Xia, T.; Hoek, E. M. V.;
Tam, P. K. H.; Chiu, J. F.; Che, C. M. Silver nanoparticles: Partial Somasundaran, P.; Klaessig, F.; Castranova, V.; Thompson, M.
oxidation and antibacterial activities. JBIC, J. Biol. Inorg. Chem. 2007, Understanding biophysicochemical interactions at the nano-bio
12, 527−534. interface. Nat. Mater. 2009, 8, 543−557.
(23) Liu, Y. Q.; Majetich, S. A.; Tilton, R. D.; Sholl, D. S.; Lowry, G. (43) Lundqvist, M.; Stigler, J.; Elia, G.; Lynch, I.; Cedervall, T.;
V. TCE dechlorination rates, pathways, and efficiency of nanoscale Dawson, K. A. Nanoparticle size and surface properties determine the
iron particles with different properties. Environ. Sci. Technol. 2005, 39, protein corona with possible implications for biological impacts. Proc.
1338−1345. Natl. Acad. Sci. U.S.A. 2008, 105, 14265−14270.
(24) Baalousha, M.; Le Coustumer, P.; Jones, I.; Lead, J. R. (44) Lynch, I.; Dawson, K. A. Protein-nanoparticle interactions. Nano
Characterisation of structural and surface speciation of representative Today 2008, 3, 40−47.
commercially available cerium oxide nanoparticles. Environ. Chem. (45) Kim, H. J.; Phenrat, T.; Tilton, R. D.; Lowry, G. V. Fe(0)
2010, 7, 377−385. nanoparticles remain mobile in porous media after aging due to slow
(25) Derfus, A. M.; Chan, W. C. W.; Bhatia, S. N. Probing the desorption of polymeric surface modifiers. Environ. Sci. Technol. 2009,
cytotoxicity of semiconductor quantum dots. Nano Lett. 2004, 4, 11− 43, 3824−3830.
18. (46) Walczyk, D.; Bombelli, F. B.; Monopoli, M. P.; Lynch, I.;
(26) Hou, W. C.; Jafvert, C. T. Photochemical transformation of Dawson, K. A. What the cell “Sees” in bionanoscience. J. Am. Chem.
aqueous c(60) clusters in sunlight. Environ. Sci. Technol. 2009, 43, Soc. 2010, 132, 5761−5768.
362−367. (47) Cumberland, S. A.; Lead, J. R. Particle size distributions of silver
(27) Cheng, Y. W.; Yin, L. Y.; Lin, S. H.; Wiesner, M.; Bernhardt, E.; nanoparticles at environmentally relevant conditions. J .Chromatogr., A
Liu, J. Toxicity reduction of polymer-stabilized silver nanoparticles by 2009, 1216, 9099−9105.
sunlight. J. Phys. Chem. C 2011, 115, 4425−4432. (48) Baalousha, M.; Manciulea, A.; Cumberland, S.; Kendall, K.;
(28) Chen, C. Y.; Jafvert, C. T. The role of surface functionalization Lead, J. R. Aggregation and surface properties of iron oxide
in the solar light-induced production of reactive oxygen species by nanoparticles: Influence of ph and natural organic matter. Environ.
single-walled carbon nanotubes in water. Carbon 2011, 49, 5099− Toxicol. Chem. 2008, 27, 1875−1882.
5106. (49) Hitchman, A.; Ju-Nam, Y.; Sambrook-Smith, G.; Sterling, G. M.;
(29) Reinsch, B. C.; Levard, C.; Li, Z.; Ma, R.; Wise, A.; Gregory, K. Lead, J. R. The effect of environmentally relevant conditions on PVP
B.; Brown, J.; G., E.; Lowry, G. V. Sulfidation of silver nanoparticles stabilised gold nanoparticles. Chemosphere 2012, in press.
decreases Escherichia coli growth inhibition. Environ. Sci. Technol. 2012, (50) Stankus, D. P.; Lohse, S. E.; Hutchison, J. E.; Nason, J. A.
46, No. 10.1021/es203732x. Interactions between natural organic matter and gold nanoparticles
(30) Ma, R.; Levard, C.; Marinakos, S.; Chen, Y.; Liu, J.; Brown, G. stabilized with different organic capping agents. Environ. Sci. Technol.
E., Jr.; Lowry, G. V. Size controlled dissolution of silver nanoparticles. 2011, 45, 3238−3244.
Environ. Sci. Technol. 2012, 46, 752−759. (51) Li, Z.; Greden, K.; Alvarez, P. J. J.; Gregory, K. B.; Lowry, G. V.
(31) Phenrat, T.; Song, J. E.; Cisneros, C. M.; Schoenfelder, D. P.; Adsorbed polymer and nom limits adhesion and toxicity of nano scale
Tilton, R. D.; Lowry, G. V. Estimating attachment of nano- and zerovalent iron to E. coli. Environ. Sci. Technol. 2010, 44, 3462−3467.
submicrometer-particles coated with organic macromolecules in (52) Kaegi, R.; Voegelin, A.; Sinnet, B.; Zuleeg, S.; Hagendorfer, H.;
porous media: Development of an empirical model. Environ. Sci. Burkhardt, M.; Siegrist, H. Behavior of metallic silver nanoparticles in a
Technol. 2010, 44, 4531−4538. pilot wastewater treatment plant. Environ. Sci. Technol. 2011, 45,
(32) Deonarine, A.; Lau, B. L. T.; Aiken, G. R.; Ryan, J. N.; Hsu-Kim, 3902−3908.
H. Effects of humic substances on precipitation and aggregation of zinc (53) Lundqvist, M.; Stigler, J.; Cedervall, T.; Berggard, T.; Flanagan,
sulfide nanoparticles. Environ. Sci. Technol. 2011, 45, 3217−3223. M. B.; Lynch, I.; Elia, G.; Dawson, K. The evolution of the protein
(33) Fauconnier, N.; Pons, J. N.; Roger, J.; Bee, A. Thiolation of corona around nanoparticles: A test study. ACS Nano 2011, 5, 7503−
maghemite nanoparticles by dimercaptosuccinic acid. J. Colloid 7509.
Interface Sci. 1997, 194, 427−433.
(34) Lee, J.; Donahue, N. M. Secondary organic aerosol coating of
synthetic metal-oxide nanoparticles. Environ. Sci. Technol. 2011, 45,
4689−4695.
(35) Phenrat, T.; Saleh, N.; Sirk, K.; Tilton, R. D.; Lowry, G. V.
Aggregation and sedimentation of aqueous nanoscale zerovalent iron
dispersions. Environ. Sci. Technol. 2007, 41, 284−290.
(36) Hotze, E. M.; Phenrat, T.; Lowry, G. V. Nanoparticle
aggregation: Challenges to understanding transport and reactivity in
the environment. J. Environ. Qual. 2010, 39, 1909−1924.
(37) Hotze, E. M.; Bottero, J. Y.; Wiesner, M. R. Theoretical
framework for nanoparticle reactivity as a function of aggregation state.
Langmuir 2010, 26, 11170−11175.
(38) Richter, K.; Schicklberger, M.; Gescher, J. Dissimilatory
reduction of extracellular electron acceptors in anaerobic respiration.
Appl. Environ. Microbiol. 2012, 78, 913−921.
(39) Law, N.; Ansari, S.; Livens, F. R.; Renshaw, J. C.; Lloyd, J. R.
Formation of nanoscale elemental silver particles via enzymatic
reduction by Geobacter sulf urreducens. Appl. Environ. Microbiol. 2008,
74, 7090−7093.
(40) Allen, B. L.; Kichambare, P. D.; Gou, P.; Vlasova, II; Kapralov,
A. A.; Konduru, N.; Kagan, V. E.; Star, A. Biodegradation of single-
walled carbon nanotubes through enzymatic catalysis. Nano Lett. 2008,
8, 3899−3903.
(41) Kang, S.; Mauter, M. S.; Elimelech, M. Physicochemical
determinants of multiwalled carbon nanotube bacterial cytotoxicity.
Environ. Sci. Technol. 2008, 42, 7528−7534.

6899 dx.doi.org/10.1021/es300839e | Environ. Sci. Technol. 2012, 46, 6893−6899

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