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To date, only a small fraction of site reme important considering that more than half of currently used to clean up contaminated
diation has been conducted by the U.S. EPA. the U.S. population relies on groundwater for groundwater is the permeable reactive barrier
Most cleanup is funded by public and private drinking. Once groundwater is polluted, its (PRB). PRBs are treatment zones composed
property owners who are potentially respon remediation is often protracted, costly, and of materials that degrade or immobilize con
sible for the contamination (U.S. EPA 2004). sometimes infeasible. taminants as the groundwater passes through
The U.S. EPA (2004) estimated that it will Pump and treat. Early treatment rem the barrier. They can be installed as perma
take 30–35 years and cost up to $250 bil edies for groundwater contamination were nent, semipermanent, or replaceable barriers
lion to clean up the nation’s hazardous waste primarily pump-and-treat operations. This within the flow path of a contaminant plume.
sites. The U.S. EPA (2004) anticipates that method involves extracting contaminated The material chosen for the barrier is based
these high costs will provide an incentive to groundwater via wells or trenches and treat on the contaminant(s) of concern (U.S. EPA
develop and implement cleanup approaches ing the groundwater above ground (ex situ) 2001). One drawback of PRBs is that they
and technologies that will result in “better, using processes such as air stripping, carbon can only remediate contaminant plumes that
cheaper, and faster site cleanups.” Developing adsorption, biological reactors, or chemical pass through them; they do not address dense
cost-effective, in situ groundwater treatment precipitation (U.S. EPA 2001). Many of these NAPLs (DNAPLs) or contaminated ground
technologies could save billions of dollars in processes produce highly contaminated wastes water that is beyond the barrier.
cleanup costs. that then have to be disposed. Other in situ treatment technologies include
Figure 1A shows U.S. EPA estimates of The U.S. EPA (2001) studied the aver thermal treatment (steam-enhanced extraction,
the total number of hazardous waste sites in age operating costs of pump-and-treat sys electrical resistive heating, or thermal conduc
the United States (U.S. EPA 2004). State and tems at 32 Superfund-financed sites and tive heating), chemical oxidation, surfactant
private property owners make up the larg found the annual cost to be approximately cosolvent flushing, and bioremediation.
est percentage (51%), followed by sites with $767,000/site. The average pump-and-treat Because of the high cost and lengthy oper
underground storage tanks (43%). Together, system operated for 5 years, treating an aver ating periods for pump-and-treat remedies,
they account for nearly 94% of all hazard age 118 million gallons of water per site for use of in situ groundwater treatment technolo
ous waste sites in the United States. Most of an average cost of $9.4 million to clean up a gies is increasing. Remedies selected for NPL
these sites have similar contaminants, such as single site (U.S. EPA 2001). Many of these sites are documented in records of decision
solvents and other organics, metals, and petro sites have ongoing monitoring, which con (RODs). A ROD provides the justification
leum products. Although DOD and DOE tinues to incur annual operating costs. Sites for the remedial action (treatment) chosen at a
sites constitute < 4% of the total number of contaminated with nonaqueous-phase liquids Superfund site. The percentage of RODs that
sites, they tend to be larger and more complex. (NAPLs) tend to operate for longer periods selected in situ groundwater treatment went
Figure 1B shows estimates for the total cleanup of time, incurring even higher average costs from zero in fiscal years 1982–1986 to 31% in
costs associated with these sites. Although state (U.S. EPA 2004). fiscal year 2005. RODs that select pump and
and private-party sites make up 51% of the Pump-and-treat projects represent the largest treat (ex situ) alone have decreased from about
total hazardous waste sites, they represent only number of treatments at Superfund sites, 38% 80% before fiscal year 1992 to an average of
14% of the total costs. Most of the estimated (725 of 1,915). Of the 1,915 treatment remedies 20% during fiscal years 2001–2005 (U.S. EPA
costs to remediate U.S. hazardous wastes sites tracked by the U.S. EPA, 36% (687 projects) 2008a). Ex situ remediation techniques could
are borne by RCRA‑CA (21%), DOE (17%), have been completed or shut down. However, be phased out over the coming decade.
and DOD (16%) sites. Together, these add up only 11% of these 687 projects are pump-and-
to $89 billion, or 54% of the total market. treat projects (U.S. EPA 2008a). Nanoremediation
More than 80% of NPL sites have con In situ remediation. A common type of Nanoremediation methods entail the appli
taminated groundwater. This is particularly in situ, or below-ground, remediation method cation of reactive nanomaterials for trans
formation and detoxification of pollutants.
NPL RCRA-CA These nanom aterials have properties that
DOE Civilian
736 (0%) 3,800 (1%) enable both chemical reduction and cataly
35 (17%) agencies
19 (9%) sis to mitigate the pollutants of concern. For
UST 125,000
(43%)
nanoremediation in situ, no groundwater is
States and
private
pumped out for above-ground treatment, and
DOD no soil is transported to other places for treat
33 (16%) 30 (14%)
ment and disposal (Otto et al. 2008).
Nanomaterials have highly desired prop
erties for in situ applications. Because of their
minute size and innovative surface coatings,
nanoparticles may be able to pervade very
small spaces in the subsurface and remain sus
UST
pended in groundwater, allowing the particles
16 (8%)
to travel farther than larger, macro-sized parti
NPL cles and achieve wider distribution. However,
States and DOD 32 (15%) in practice, current nanomaterials used for
private 6,400 (2%) RCRA-CA remediation do not move very far from their
150,000 Civilian 45 (21%)
DOE injection point (Tratnyek and Johnson 2006).
(51%) agencies
5,000 (2%) Many different nanoscale materials have
3,000 (1%)
been explored for remediation, such as nano
Total no. of sites = 294,000 Total = $209 billion scale zeolites, metal oxides, carbon nanotubes
Figure 1. Estimated number (%) of U.S. hazardous waste sites (A) and estimated cleanup costs [billions and fibers, enzymes, various noble metals
US$ (percent of total)] for 2004–2033 (B). UST, underground storage tanks. Adapted from U.S. EPA (2004). [mainly as bimetallic nanoparticles (BNPs)],
and titanium dioxide. Of these, nanoscale and detoxification of a variety of common Initially, Fe nanoparticles have a core of
zero-valent iron (nZVI) is currently the most environmental pollutants, including chlori ZVI and an outer shell of Fe oxides, which
widely used. The different nanomaterials, along nated organic solvents, organochlorine pesti suggest the following redox reactions:
with the pollutants they could potentially cides, and polychlorinated biphenyls (PCBs).
remediate, are listed in Supplemental Material, According to Zhang (2003), Fe-mediated Fe0(s) + 2H2O(aq) →
Table 1, available online (doi:10.1289/ reactions should produce an increase in pH Fe2+(aq) + H2(g) + 2OH–(aq)
ehp.0900793.S1 via http://dx.doi.org/). [For a and a decrease in the solution redox potential 2Fe0(s) + 4H+(aq) + O2(aq) →
comprehensive overview of the chemistry and created by the rapid consumption of oxygen, 2Fe2+(aq) + 2H2O(l),
engineering of various nanotechnology appli other potential oxidants, and the production
cations addressed in Supplemental Material, of hydrogen. Although batch reactors pro where s is solid, aq is aqueous, g is gas, and l is
Table 1, and used for remediation, see Theron duce pH increases of 2–3 and an oxidation– liquid (Matheson and Tratnyek 1994).
et al. (2008) and Zhang (2003).] reduction potential (ORP) range of –500 to Although Fe nanop articles have been
nZVI. nZVI particles range from 10 to –900 mV, it is expected that the pH and ORP shown to have a strong tendency to form
100 nm in diameter, although some vendors would be less dramatic in field applications micros cale aggregates, possibly because of
sell micrometer-scale iron powders as “nano where other mechanisms reduce the chemical their weak surface charges, coatings can be
particles.” Typically, a noble metal (e.g., palla changes (Zhang 2003). Previous work show applied to change the surface properties. These
dium, silver, copper) can be added as a catalyst. ing an increase of pH by 1 and an ORP in the different forms of Fe could be useful for the
The second metal creates a catalytic synergy range of –300 to –500 mV supports this assess separation and transformation of a variety of
between itself and Fe and also aids in the ment (Elliott and Zhang 2001; Glazier et al. contaminants, such as chlorinated organic
nanoparticles’ distribution and mobility once 2003). Zhang (2003) also showed that modify solvents, organochlorine pesticides, PCBs,
injected into the ground (Saleh et al. 2007; ing Fe nanoparticles could enhance the speed organic dyes, various inorganic compounds,
Tratnyek and Johnson 2006; U.S. EPA 2008b). and efficiency of the remediation process. and the metals As(III) (trivalent arsenic),
These BNPs may contain more than two dif The first field application was reported in Pb(II) (bivalent lead), copper [Cu(II) (bivalent
ferent metals. The second metal is usually less 2000 (Zhang 2005). Nanoparticles have been copper)], Ni(II) (bivalent nickel), and Cr(VI)
reactive and is believed to promote Fe oxidation shown to remain reactive in soil and water for (hexavalent chromium) (Sun et al. 2006).
or electron transfer (U.S. EPA 2008b). Some up to 8 weeks and can flow with the ground Nanoremediation, particularly use of
noble metals, particularly palladium, catalyze water for > 20 m. In one study, Zhang (2003) nZVI, has site-specific requirements that must
dechlorination and hydrogenation and can produced a 99% reduction of TCE within a be met in order for it to be effective. Adequate
make the remediation more efficient (U.S. EPA few days of injection. site characterization is essential, including
2008b; Zhang and Elliott 2006). Because nanoscale particles are so small, information about site location, geologic con
The underlying chemistry of the reaction Brownian movement or random motion, ditions, and the concentration and types of
of Fe with environmental pollutants (par rather than wall effects, dominates their physi contaminants. Geologic, hydrogeologic, and
ticularly chlorinated solvents) has been exten cal movement or transport in water. The move subsurface conditions include composition of
sively studied and applied in micrometer-scale ment of micrometer-scale particles, especially the soil matrix, porosity, hydraulic conductiv
ZVI PRBs (Matheson and Tratnyek 1994). microscale metal particles, is largely controlled ity, groundwater gradient and flow velocity,
There are two main degradation pathways by gravity-induced sedimentation because of depth to water table, and geochemical prop
for chlorinated solvents: beta elimination their size and high density. In the absence of erties (pH, ionic strength, dissolved oxygen,
and reductive chlorination. Beta elimination significant surface electrostatic forces, nano- ORP, and concentrations of nitrate, nitrite,
occurs most frequently when the contaminant sized particles can be easily suspended in water and sulfate). All of these variables need to be
comes into direct contact with the Fe particle. during the design and manufacturing stages, evaluated before nanoparticles are injected to
The following example shows the pathway of thus providing a versatile remediation tool determine whether the particles can infiltrate
trichloroethene (TCE): that allows direct injection as a liquid into the the remediation source zone, and whether
subsurface where contaminants are present. the conditions are favorable for reductive
TCE + Fe0 → Coating the Fe particles to improve mobility transformation of contaminants. The sorp
Hydrocarbon products + Cl– + Fe2+/Fe3+. and catalytic reaction rates is important. Some tion or attachment of nanoparticles to soil
Under reducing conditions fostered by of the particles flow with the groundwater and and aquifer materials depends on the surface
nZVI in groundwater, the following reaction remain in suspension for various amounts of chemistry (i.e., electrical charge) of soil and
takes place: time, whereas others are filtered out and bind nanoparticles, groundwater chemistry (e.g.,
to soil particles, providing an in situ treatment ionic strength, pH, and presence of natural
PCE → TCE → DCE → VC → ethene, zone that could hold back emanating plumes organic matter), and hydrodynamic condi
where PCE is perchloroethylene, DCE is (Henn and Waddill 2006). tions (pore size, porosity, flow velocity, and
dichloroethylene, and VC is vinyl chloride The high reactivity of nZVI particles is in degree of mixing or turbulence). The reac
(Tratnyek 2003, U.S. EPA 2008b). part a direct result of their high specific surface tions between the contaminants and the nZVI
In the 1990s, Fe at the nanos cale was area. For example, nZVI produced by the boro depend on contact or probability of contact
synthesized from Fe(II) and Fe(III) to pro hydride method has surface areas in the range of between the pollutant and nanoparticles (U.S.
duce particles ranging from 10 to 100 nm, 20–40 m2/g, which can yield 10–1,000 times EPA 2007, 2008b).
initially using borohydride as the reductant, greater reactivity compared with granular Fe, In field tests, Henn and Waddill (2006)
and examined in laboratory studies. Zhang which has a surface area < 1 m2/g (Wang and found that, with the use of nZVI, decreases
(2003) tested nZVI for the transformation of Zhang 1997). nZVI’s small particle size also in parent pollutant compound concentrations
a large number of pollutants, most notably allows more of the material to penetrate into (TCE and trichloroethane) were accompa
halogenated organic compounds commonly soil pores, and it can be more easily injected nied by increases and subsequent decreases in
detected in contaminated soil and groundwa into shallow and deep aquifers, a property that daughter product concentrations (cis-1,2-DCE,
ter. The author reported that nanoscale Fe par is particularly beneficial when contamination 1,1-dichloroacetic acid, 1,1-DCE, and vinyl
ticles are very effective for the transformation lies underneath a building. chloride). Long-term observations indicated
that although the degradation was continuous, tests have shown 99% removal of As using contaminant diffuses into the interior of the
it was at a much slower rate for the daughter 12‑nm-diameter Fe oxide nanop articles emulsion droplet, where it comes into contact
products. Their study concluded that there was (Rickerby and Morrison 2007). Kanel et al. with the ZVI and is degraded. A concentra
overall reduction in contaminants, a reduced (2006) concluded that nZVI can reduce As(V) tion gradient is established by migration of the
plume size, and reduction in the contaminant to As(III) in a short period of time at neu TCE molecules into the interior aqueous phase
mass flux emanating from the source. The tral pH. They also found that a high amount of the emulsion droplet and by migration of
nanoscale Fe created conditions for abiotic of nZVI was needed to completely remove the by-products out of the droplet and into the
degradation for about 6–9 months, followed As(V), possibly because of the presence of dis surrounding water phase, further driving the
by biological degradation as the primary degra solved organic carbon, sulfate, and phosphate. degradation reactions (O’Hara et al. 2006).
dation process. Both processes had significant The hydrophilic properties of nZVI In other field test research conducted
impacts on the degradation of contaminants enable the remediation of aqueous-phase con between 2003 and 2005 in North America
(Henn and Waddill 2006). Cao et al. (2005) taminants, including DNAPLs. Because the and Europe, nZVI was effective in treating
found that nZVI particles in an aqueous solu addition of nZVI in the source zone reduces various compounds in groundwater, including
tion reduced perchlorate to chloride almost contaminants, it increases the concentra chlorinated solvents and Cr(VI) (Macé et al.
completely without producing intermediate tion gradient between the aqueous phase 2006). These field tests showed that the con
degradation products. and DNAPLs, thereby increasing the mass centrations of chlorinated solvents decreased
Fe oxide nanoparticles have been shown to transfer of contaminants from DNAPLs to dramatically during the first few hours and
bind As irreversibly up to 10 times more effec the dissolved aqueous phase, where they are days after injection and remained low in con
tively than micrometer-sized particles. Based then treated (Watlington 2005). To address junction with the mass balance of nZVI ver
on their super-paramagnetic properties, the Fe DNAPLs directly, emulsified ZVI (eZVI) sus the mass of chlorinated hydrocarbons in
particles and bound As can be separated from has been used. When the emulsion droplets the remediation area. When present, sulfates
the water with a magnetic field. Laboratory come into contact with dissolved TCE, the and nitrates also decreased in parallel with the
chlorinated solvents, but diminished the effect
of nZVI on other solvents.
Macé et al. (2006) found that nZVI
moved with groundwater away from the
injection site. Based on this, they hypothe
sized that nZVI could treat larger areas of the
affected aquifers. They found dramatic but
short-lived reductions of volatile organic com
pounds (VOCs) in fractured bedrock and a
slower, steadier decrease of VOCs in primary
porosity aquifers. The same study suggested
that the degradation of VOCs and travel
velocity are indirectly proportional to the
hydraulic conductivity. BNPs reacted more
quickly and were spent more rapidly than
nZVI, whereas nZVI reacted more slowly but
had a longer effect. Macé et al. (2006) noted
minor but inconclusive changes to the micro
bial community due to the addition of nano
Figure 2. Map of remediation sites listed in Supplemental Material, Table 2 (doi:10.1289/ehp.0900793.S1)
(Project on Emerging Nanotechnologies 2009). particles. These changes could affect parallel
bioremediation.
In an extensive study, the Navy con
Type of nanoparticles used Type of media treated ducted field tests using nZVI to remedi
Nano-oxide Soil ate two of its contaminated sites (Naval Air
2% 2% Groundwater Engineering Station, Lakehurst, NJ, and
Unknown
20% 60%
Naval Air Station, Jacksonville, FL) and
BNP
29% Sands and using micrometer-sized ZVI powder at a
clayey silts third site, Hunters Point Shipyard, Hunters
2%
Point, California (Gavaskar et al. 2005). In
the Jacksonville study, TCE concentrations
in a well approximately 20 ft from the source
zone were reduced up to 99%, suggesting that
some of the nZVI migrated outside of the
treatment zone through preferential pathways.
Long-term monitoring of the treatment zone
Soil and
groundwater
was recommended to demonstrate that the
16% decline in parent compounds (e.g., TCE) and
eZVI by‑products (e.g., cis‑1,2‑DCE) persists after
9% nZVI the ZVI is depleted, which will permit deter
60% mination of how much, if any, DNAPL mass
Figure 3. Type of nanoparticles used (A) and type of media treated (B) at sites listed in Supplemental truly remains in the treatment zone (Gavaskar
Material, Table 2 (doi:10.1289/ehp.0900793.S1). et al. 2005).
In addition to groundwater remediation, performance, cost, and environmental aspects, Potential Implications
nanotechnology holds promise in reducing thereby providing site managers and other Fate and transport. When released into the
the presence of NAPLs. Recently, a material stakeholders with additional information to environment, manufactured nanop articles
using nano-sized oxides (mostly calcium) was determine whether the technology might be aggregate to some degree and behave like
used in situ to clean up heating oil spills from applicable to their specific sites. natural nanomaterials. However, to be effec
underground oil tanks. Preliminary results PARS Environmental Inc. (2004) con tive, nZVI needs to form stable dispersions in
from this redox-based technology suggest ducted a case-study cost comparison of water so it can be delivered to water-saturated
faster, cheaper methods and, ultimately, lower a manufacturing site in New Jersey where porous material in the contaminated area.
overall contaminant levels compared with pre the primary contaminants of concern were Yet, its rapid aggregation limits its mobility
vious remediation methods. Most of these sites TCE and PCE. They estimated that using the (Phenrat et al. 2007). The rapid aggregation
have been in New Jersey, with cleanup con pump-and-treat method would cost approxi of the nanoscale Fe particles supports the need
ducted in consultation with the New Jersey mately $4,160,000 and PRB approximately for polymer or other coatings to modify the
Department of Environmental Protection (see $2,200,000. nZVI would cost approximately nZVI surface in order to improve mobility
Continental Remediation LLC 2009). $450,000, representing a cost savings of (Phenrat et al. 2007).
The state of the practice. The number of 80–90% over the pump-and-treat method. Depending on the composition of ground
actual applications of nZVI is increasing rap Table 1 indicates the relative magnitude water and the hydrologic conditions, certain
idly. Only a fraction of the projects has been of the media and contaminant group at four nanoscale colloids have the ability to travel
reported, and new projects show up regularly. types of remediation sites. Using Table 1 unexpectedly large distances in the environ
Figure 2 and Supplemental Material, Table 2 and Figure 1B, the cost savings to remedi ment (Kersting et al. 1999; Novikov et al.
(doi:10.1289/ehp.0900793.S1) describe 44 ate groundwater can be estimated for NPL, 2006; Vilks et al. 1997). They could form
sites where nanoremediation methods have RCRA, DOD, and DOE sites. Using nano stable nanoclusters in groundwater that are
been tested for site remediation. These sites remediation, potential savings of $87 billion likely to be highly mobile, carrying with them
are in seven countries (including the United to $98 billion can be realized to clean up the surface-sorbed contaminants. These natural
States) and in 12 U.S. states. All of the sites nation’s hazardous waste sites over the next particles can carry materials between redox
have some form of chlorinated compounds 30 years. Although this estimate is based on zones and facilitate or inhibit contaminant
of concern, such as PCE, TCE, or PCBs. publicly available data and assumes use of transport (Waite et al. 1999).
Other pollutants include Cr(VI) and nitrate. nZVI or a variation of nanoremediation for The mobility of natural or synthetic nano
The sites include oil fields, manufacturing all sites with contaminated groundwater, it particles in the natural environment will
sites, military installations, private properties, is a reasonable estimate of the magnitude of strongly depend on whether the nanoparticles
and residences. cost savings achievable using this technol remain completely dispersed, aggregate and
Figure 3A shows the types of manufac ogy. Increased manufacturing capacity to settle, or form mobile nanoclusters. Gilbert
tured nanoparticles used for remediation at supply the amount of nanomaterials needed et al. (2007) suggested that many manufac
the sites. More than two-thirds of the sites could lead to lower costs from economies of tured metal oxide and other inorganic nano
are treated with a form of ZVI, and most of scale. It should be noted, however, that not particles will exhibit cluster-forming behavior
the BNPs contain Fe. Figure 3B shows the all sites have conditions suitable for nanoscale similar to that of natural nanoparticles. Despite
types of media treated at these sites. More remediation methods. numerous observations that nanoscale minerals
than three-fourths of the sites treated contain In addition to the potential cost savings represent an important fraction of the environ
contaminated groundwater. associated with using nanotechnology for site mental colloids, the fundamental aggregation
Supplemental Material, Table 2 (doi:10. remediation, the amount of time required and transport properties of nanoparticles have
1289/e hp.0900793.S1) lists details of the to clean up a site could be greatly reduced. not been extensively studied.
44 sites treated with nanomaterials and the The average pump-and-treat system operates In addition to self-aggregation, nano
results of the treatment. Because data from for about 18 years (U.S. EPA 2001). In a particles could associate with suspended solids
most of these sites were not collected as part of study using nZVI, Zhang (2003) observed a or sediment, where they could bioaccumulate
a research project, the information is general 99% reduction in TCE levels within days of and enter the food chain or drinking water
and, in most cases, incomplete. For example, injection. This shortened time interval not sources. These fate processes depend on both
site 2 is a BP Global site in Alaska contami only reduces operating costs but also reduces the characteristics of the particle and the char
nated with trichloroethane; when BNPs were the time that workers are exposed to a con acteristics of the environmental system (Boxall
used, practitioners saw reductions of 60% taminated site during cleanup. Environmental et al. 2007).
and 90% for shallow test and deep test con disturbances that can affect the local eco The use of nanoparticles in environmental
centrations, respectively. At site 11, in the system’s flora, fauna, and microorganisms are remediation will inevitably lead to the release
Czech Republic, nZVI was used to reduce reduced because nZVI is injected using small of nanoparticles into the environment and
chlorinated solvents. Levels were reduced wells instead of excavating soils or removing subsequent ecosystems. To understand and
to an order of magnitude lower than origi groundwater using pump-and-treat methods; quantify the potential risks, the mobility,
nal concentrations and were maintained for the time of site disturbance is also shorter. bioavailability, toxicity, and persistence of
6 months. Supplemental Material, Table 2,
provides an overview of the current state of Table 1. Percentage of total sites being remediated with respect to each media and contaminant group
the practice using nanomaterials, mainly ZVI, (U.S. EPA 2004).
for site remediation. Media Contaminant group
Because many of the remediation projects Type of site Groundwater Soil Sediment VOCs Metals SVOCs
using nanoparticles are just beginning or are NPL 83 78 32 78 77 71
ongoing, cost and performance data are lim RCRA-CA 82 61 6 67 46 32
ited. However, as the technology is applied DOD 63 77 18 64 72 57
at an increasing number of sites with varying DOE 72 72 72 38 55 38
geologies, more data will become available on SVOCs, semivolatile VOCs.
manufactured nanoparticles need to be stud of the organism being exposed (Dhawan et al. and oxidative protein damage in vivo (Valko
ied (Nowack 2008). To pose a risk, nano 2006). Although available data indicate that et al. 2005).
particles must be hazardous and have a route current risks of manufactured nanoparticles Particle coating, surface treatments, surface
for exposure. Although aggregated and/or in the environment to environmental and excitation by ultraviolet radiation, and particle
absorbed nanoparticles are usually less mobile, human health are probably low (see Table 3 in aggregation can modify the effects of particle
they still have the potential to be taken up Boxall et al. 2007), knowledge of their poten size, suggesting that some nanoparticles could
by filter feeders and other sediment-dwelling tial impact in the environment and on human exert their toxic effects as aggregates or through
organisms. The U.S. EPA has raised the pos health is still limited. the release of toxic chemicals (Nel et al. 2006).
sibility of biomagnification of nanoparticles; Research on ultrafine particulates Although the aggregates are fractal-like, they
however, no data currently exist proving or (< 100 nm in one dimension) has shown that may exhibit some of the properties of the dis
disproving this hypothesis (Biswas and Wu as particle size decreases, potential for pul crete nanoparticles, including specific surface
2005; U.S. EPA 2007). To be able to quan monary toxicity tends to increase even if the area and reactivity, particularly because these
tify the stability of nanoparticles in the envi material’s larger form is inert. nZVI is typically particles have been manufactured at the nano
ronment, the stability of their suspensions between tens and hundreds of nanometers in scale in order to harness particular nanoscale
and their tendency to aggregate and interact size at the time of production. Under labora properties.
with other particles must first be determined tory conditions, these particles tend to aggre Generally, little concern has been raised
(Mackay et al. 2006). gate and produce clusters that can build up to about the toxicity of nZVI because Fe oxides
Potential toxicity. Naturally occurring the micrometer size. If this occurs, they will formed during remediation are already pres
nanoscale Fe oxide particles with metals (such not take on the properties that apply to actual ent in the form of rust and because the nano-
as copper) bound to their surface have been nanosized particles and will behave similarly to Fe particles have not been found to produce
found many kilometers downstream from larger environmental colloids (Tratnyek and radically new properties, compared with
mining sites, indicating the ability of these Johnson 2006). microscale-sized Fe particles (Watlington
colloidal nanoparticles to move and transport Inhalation exposure to Fe0(s) nanoparticles 2005). Whether the addition of catalytic
sorbed contaminants (Hochella et al. 2005). could result in the release of Fe(III), followed coatings changes these properties or presents
These binding properties and processes may by oxidative damage due to generation of another hazard has yet to be determined.
show size-dependent reactivity on crystal Fe(IV) (Keenan and Sedlak 2008). In vitro Oberdörster et al. (2006) suggested that toxic
line Fe oxide nanoparticles, and each process studies examining the response of the cen ity studies should not simply focus on human
might occur with different thermochemical tral nervous system to low concentrations of and wildlife but should also examine benthic
and kinetic relationships as a function of size nano-Fe and nanomagnetite showed that these and soil flora and fauna, because they make
(Madden et al. 2006). Thus, whereas the nanoparticles are taken up into cells and pro up the basis of food chains. Biological systems
nanoparticles themselves may not possess toxic duce an oxidative stress response (Wiesner did not evolve alongside the nanoparticles
properties, the pollutants they could carry et al. 2006). These studies indicate a potential that are now being manufactured and released
with them may. Fe nanomaterials may bind for adverse health effects from exposure and (Moore 2006). Different reactions to nZVI
with and carry copper, which has a toxicity uptake of Fe oxide nanoparticles into mam may be found in some lower organisms.
threshold for algae, flowering plants, fungi, malian cells. The authors caution, however, The Royal Commission on Environmental
and phytoplankton that is surpassed only by that these tests were conducted at much higher Pollution (2008) summed up the current
mercury and sometimes silver (Sposito 1989). dosages than would be encountered normally approach to potential implications from
Handy et al. (2008) suggested that despite (Wiesner et al. 2006). nanomaterials:
the environment containing many natural par In some cases, Fe oxide nanoparticles (a While there have been no significant events that
ticles at the nanoscale, manufactured nano potential end product from redox reactions of would lead us to suppose that the contemporary
particles may act differently. These materials nZVI) can be internalized by cells and cause introduction of novel materials is a source of
are designed to have specific surface properties cell death. Low solubility of Fe oxide nano environmental hazard, we are acutely aware of
and chemistries that are not likely to be found particles enables them to persist in biological past instances where new chemicals and products,
originally thought to be entirely benign, turned
in natural particles. The properties of manu systems and could potentially induce long- out to have very high environmental and public
factured nanoparticles enhance novel physico term effects involving mutagenic influence health costs.
chemical and possibly toxicologic properties on organisms (Auffan et al. 2006). However,
compared with natural particles. A range of there are limited data on the interactions of Societal Issues
ecotoxicologic effects of various manufactured Fe oxide nanoparticles with cells and the effect
nanomaterials has been reported, including that coatings can have on cell adhesion, inter Most societal issues are based on the unknown
effects on microbes, plants, invertebrates, and nalization, and interaction. risks of using nanoscale materials for site reme
fish (Boxall et al. 2007). Laboratory stud Mineral nanoparticles are common com diation. At one end of the spectrum, some non
ies using fish, Daphnia, copepods, and other ponents of natural aqueous systems. Several governmental groups invoked the precautionary
organisms (Adams et al. 2006; Fortner et al. natural inorganic and biologically mediated principle in an attempt to halt all use of the
2005; Lovern et al. 2007; Oberdörster et al. processes produce mineral nanoparticles, such technology until proven safe. In early 2003,
2006) have shown that these organisms can as metal sulfides and metal oxides (Labrenz the ETC Group called for the precautionary
take up some manufactured nanoparticles. et al. 2000; Villalobos et al. 2003). Nanoscale principle to be applied to nanotechnology
The factors and processes affecting eco Fe (oxy)hydroxide phases are among the (ETC Group 2003). They based their concerns
toxicity are complex, and the impact of most common natural mineral nanoparticles on Eric Drexler’s concept of multiple nano
manufactured nanoparticles on organisms is formed by precipitation from solution after scale machines that might self-replicate and
determined by a range of properties, including oxidation of aqueous ferrous Fe (Van der change matter into “gray goo” (Drexler 1986).
dissolution potential, aggregation potential, Zee et al. 2003). Although Fe is an essen Drexler later clarified this image (Phoenix and
particle surface properties, the characteristics tial element for growth in nearly all species, Drexler 2004), but not before Prince Charles of
of the exposure environment, and the bio an abundance of free chelating Fe has been England became concerned enough about the
chemical, physiological, and behavioral traits linked to DNA damage, lipid peroxidation, risks of nanotechnology to ask the Royal Society
to examine the implications of nanotechnology. The consensus is caution, not precaution, and, which organisms in the ecosystem and humans
In one part of their report (Royal Society and in the absence of definitive risk data, the tech might be exposed to them.
Royal Academy of Engineering 2004), the nology is generally viewed as more beneficial The properties that can be harmful to the
Royal Society came out strongly against the use than harmful. environment are the very same properties that
of nanomaterials for remediation. are advantageous and exploited during treat
Recommendations ment and remediation regimes. For instance,
We recommend that the use of free (that is, not
fixed in the matrix) manufactured nanoparticles Develop analytical tools to measure and the catalytic properties of nanoparticles that
and environmental applications such as remedia monitor manufactured nanoparticles in the induce the degradation of pollutants can also
tion be prohibited until appropriate research has environment. Currently, standard meth induce a toxic response when taken up by
been undertaken and it can be demonstrated that ods to readily detect and monitor nano cells. In addition, the high sorption capacity
the potential benefits outweigh the potential risks.
particles in the environment do not exist. of nanoparticles that is used to remove organic
In contrast, the European Commission’s There are only a few quantitative analytical and inorganic pollutants from groundwater
Scientific Committee on Emerging and Newly techniques for measuring nanoparticles in may also sequester and transport other pol
Identified Health Risks in 2005 (European environmental systems, and most of these lutants in the environment (Nowack 2008).
Commission 2005) listed environmental reme are time-consuming and require expensive As such, more work is needed on transfers in
diation technology as one of nanotechnology’s equipment and expertise. Because there is no environmental systems, for example, from the
benefits. This group also called for risk-related regulatory requirement to monitor environ environment to the organism and throughout
research. mental nanoparticles, or other particles such the trophic structure.
In a position paper, the Québec as those in drinking water, there is a critical Further research is needed to develop and
Commission (Commission de l’Ethique de la lack of data and information about the occur understand the mechanisms affecting the fate
Science et la Technologie 2006) indicated that rence and fate of nanoparticles once they are and transport of manufactured nanoparticles
[T]he biggest source of potential environmental released into the environment. Some models in water, soil, and sediments; their interac
exposure is the use of nanoparticles in sanitizing and extrapolations attempt to quantify the tions with each other, other manufactured
contaminated groundwater and soil; concerns have amount of nanoparticles in various environ nanoparticles, suspended solids, and dissolved
been raised about the impact the high reactivity mental systems. However, these models are organic material; and how these interactions
of nanoparticles might have on plants, animals, based on estimates of nanoparticles released are influenced by different environmental
micro-organisms, and ecosystems.
into the environment and have not been cali variables. The potential for manufactured
The report noted “the importance of increasing brated with actual measurements in the field nanoparticles to act as carriers for other envi
the amount of research on the potential envi (Mueller and Nowack 2008). It is difficult, ronmental contaminants also requires further
ronmental consequences of nanotechnology in if not impossible, to extrapolate the toxicity examination.
order to determine which substances may be and pathology of nanoparticles at the eco Improve engineering applications using
hazardous.” Other risk framework documents system level until sufficient baseline data on nanotechnology for in situ remediation. There
have recommended research into the toxicity, these particles are gathered (Moore 2006). is a need to develop “smarter” nanomaterials
fate and transport, and bioaccumulation of There are also no biomarkers that can be used for remediation. For example, new coatings
released nanomaterials (Maynard and Aitken to track nanoparticles as part of a biological or functional groups could enhance mobil
2006). A U.S. EPA white paper (U.S. EPA monitoring program; although existing regu ity in groundwater. More sophisticated nano
2007) pointed out the positive aspects of using latory toxicity tests could be appropriate for materials may have the ability to perform
nanomaterials in environmental remediation nanoparticles, a risk analysis would not be several functions, such as catalyzing several
while also calling for research on the possible possible without proper measurement of the different pollutant reactions on the same par
negative effects. concentrations of nanoparticles in the envi ticle or interacting with both hydrophobic and
In June 2007, DuPont and Environmental ronment (Handy et al. 2008). hydrophilic pollutants. We can build in self-
Defense released their nano risk framework Increase research to evaluate the effects of termination for active nanoparticles so they
(Medley and Walsh 2007). They chose ZVI nanoparticles on the full ecosystem. Nowack become benign after their remediation function
nanop articles as a case study. After going and Bucheli (2007) concluded that results from is finished; design nanoparticles that destroy
through the steps in the framework to assess ecotoxicologic studies show that organisms are a wide spectrum of pollutants; and improve
the potential risk of using this technology, affected by certain nanoparticles under certain delivery systems for injecting nanoparticles into
DuPont (2007) decided it “would not con environmental conditions. However, the stud contaminated groundwater plumes.
sider using this technology at a DuPont site ies were conducted using elevated concentra All these engineering improvements can
until the end products of the reactions follow tions of pristine nanoparticles. The authors increase the ability of this technology to reme
ing injection, or following a spill, are deter recommended that future studies estimate diate more of the world’s hazardous waste
mined and adequately assessed.” DuPont did the exposure to functionalized nanoparticles, sites. Engineering more effective particles can
not use their full output worksheet in this case because most manufactured nanoparticles are improve the ability to reach and remediate pol
study because of the lack of environmental, functionalized, which changes their behavior. lutant plumes and minimize potential harm.
health, and safety data. Changes by environmental factors such as
Although there is no consensus among light, oxidants, and microorganisms—which Conclusions
these various reports on nanotechnology risk result in chemical or biological modifications In situ nanoremediation methods entail the
management, no doubt is expressed about the or degradation of the functionalized surface application of reactive nanom aterials for
potential efficacy of the technology. However, or coating of the surface with natural com transformation and detoxification of pollut
the concerns over safety may limit the wide pounds—are important processes that have ants in situ. These nanomaterials have proper
spread deployment of nanoremediation. The not been studied thoroughly (Nowack and ties that enable both chemical reduction and
reports cited above, as well as other published Bucheli 2007). In addition, most nanoparticles catalysis to mitigate the pollutants of concern.
reports, consistently call for research specific are released embedded in a matrix and not as No groundwater is pumped out for above-
to the possible risks of using nanotechnology single nanoparticles (Koehler et al. 2007). It is ground treatment, and no soil is transported
in environmental remediation applications. important to study nanoparticles in the form in to other places for treatment and disposal.
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