ENVIRONMENTAL ENGINEERING SCIENCE SHORT COMMUNICATION

Volume 27, Number 11, 2010

ª Mary Ann Liebert, Inc.
DOI: 10.1089/ees.2010.0141

Fullerene Nanoparticles Affect the Fate and Uptake of Trichloroethylene

in Phytoremediation Systems
Xingmao Ma* and Chen Wang
Department of Civil and Environmental Engineering, Southern Illinois University Carbondale, Carbondale, Illinois.

Received: April 30, 2010 Accepted in revised form: July 06, 2010

Abstract
Widespread applications in various industries will inevitably result in the release of a substantial amount of
carbonaceous nanoparticles into the environment. Much research has been conducted to assess their health and
environmental impacts. However, few studies have been carried out to examine the complex interactions of
carbonaceous nanoparticles with co-existing environmental pollutants in complex environmental systems. Cur-
rent work investigated the potential impacts of nC60 fullerene nanoparticles on the fate and uptake of trichloro-
ethylene by plants in phytoremediation systems. Addition of 2–15 mg/L fullerene nanoparticles did not result in
any acute toxicity to plants in terms of phenotype, water transpiration, and plant biomass in batch hydroponic
studies. Plant uptake of trichloroethylene was increased by *26% and 82% by the addition of 2 and 15 mg/L of
fullerene nanoparticles synthesized through solvent (toluene) exchange. This is the first time that fullerene na-
noparticles were shown to significantly affect the fate and uptake of an organic contaminant in phytoremediation
systems.

Key words: fullerene nanoparticles; trichloroethylene; plant uptake

Introduction (Pilon-Smith, 2005). Plant uptake is a pivotal process in de-

termining the fate of TCE in phytoremediation. Large specific

T he rapid expansion of the global market of nanotech-

nology has led to heightened interests and concerns on
the environmental consequences and implications of en-
surface area of carbonaceous nanoparticles renders them ex-
cellent adsorption materials for organic compounds (Pan and
Xing, 2008; Oleszczuk et al., 2009). Carbonaceous nano-
gineered nanoparticles (ENPs) (Rejeski, 2010). This increased particles laden with organic compounds could act as con-
attention to ENPs is particularly driven by many recent na- taminant carriers and dramatically change the fate and
notoxicity reports (Lewinski et al., 2008). ENPs are generally transport of organic compounds in various environmental
defined as intentionally manufactured particles with the size systems (Hofmann and von der Kammer, 2009). A recent
from 1–100 nm. At the nanoscale, the proportion of atoms study showed that carbon nanotubes (CNTs) can penetrate
located on the surface dramatically increase, leading to drastic the cell walls of plant root cells and provide a new mechanism
change on surface tension, electronic structure, and interfacial for enhanced uptake and accumulation of phenanthrene in
reactivity (Mauter and Elimelech, 2008). These distinctively root tissues and cell cytoplasm (Wild and Jones, 2009).
different physiochemical properties of ENPs could result in Buckminsterfullerene C60 is a carbonaceous ENP widely
highly different environmental behaviors and impacts com- used in industrial and scientific applications due to its unique
pared with their bulk counterparts. icosahedrally symmetrical structure and surface properties
In addition to direct interactions with various components (Mauter and Elimelech, 2008). In plant systems, the phyto-
of the ecosystem, ENPs can interact with co-existing con- toxic effect of fullerene C60 has not been reported, but a study
taminants, affecting their fate and transport in the environ- has demonstrated that fullerene C70 can be taken up by rice
ment (Sun et al., 2009). Trichloroethylene (TCE) is a colorless (Oryza sativa) roots and transported to shoots (Lin et al., 2009).
chlorinated solvent widespread in the environment. In phy- The objective of this study was to assess the impact of C60
toremediation systems, organic compounds such as TCE are fullerene nanoparticles on the fate and uptake of TCE in
primarily removed through enhanced rhizosphere degrada- phytoremediation systems.
tion, uptake, and phytovolatilization and phytodegradation
Materials and Methods
*Corresponding author: Department of Civil and Environmental Fullerene nanoparticle synthesis and characterization
Engineering, Southern Illinois University Carbondale, Carbondale,
IL 62901. Phone: 618-453-7774; Fax: 618-453-3044; E-mail: ma@ Fullerene nanoparticles were synthesized with the sol-
engr.siu.edu vent exchange method (Chen and Elimelech, 2006). Briefly,

989
990 MA AND WANG

0.05 g of 99.9% fullerene powder was dissolved in 20 mL high- a Teflon rubber septum and crimp top seal. Stems were cut
performance liquid-chromatography-grade toluene, forming into 1–1.5-inch smaller sections along height before they were
a magenta-colored solution. This solution was mixed with placed into 22-mL vials. The sealed vials were heated at 908C
100 mL de-ionized (DI) water and 3 mL ethanol, and the for 4 h to vaporize TCE to the headspace. TCE concentrations
mixture was then sonicated with a probe sonicator for *8 h, in the headspace were determined using a Perkin–Elmer
resulting in a yellowish fullerene nanoparticle suspension Autosystem Gas Chromatograph equipped with an electron
(SON/nC60). DI water was added periodically to compensate capture detector. The mass recovery rate of TCE was about
for the water loss in sonication. The synthesized fullerene 82%–93% (Gopalakrishnan et al. 2009).
nanoparticles were examined under a Hitachi H7650 trans-
mission electron microscope at 60 kV following established
Results and Discussion
protocols to determine the size and shape of synthesized na-
noparticles (Ma et al., 2010). The synthesized nanoparticles SON/nC60 suspension is polydisperse and the size and
were used directly without further treatment. shape characteristics of fullerene nanoparticles are in agree-
ment with literature (Brant et al., 2006). SON/nC60 is mostly
Plants and experimental setup spherical and the average size based on the measurement of a
100 nanoparticles is about 39.1 þ 11.7 nm. Fullerene particles
Twelve-inch eastern cottonwood (Populus deltoides) cut-
with diameter >100 nm were also observed. The average na-
tings, with diameter at around 1 cm, were purchased from
noparticle size was slightly smaller than reported in literature
Segal Ranch Hybrid Poplars. The plant cuttings were grown
using the same preparation method, likely due to the pro-
in a greenhouse where temperature ranged from 20.78C to
longed sonication period in this study. Four days after syn-
36.28C and the humidity from 39% to 80% during the period
thesized nanoparticles were exposed to plants and TCE, both
of this experiment. The cuttings were planted in 500-mL wide-
individual and aggregated nanoparticles could be detected.
mouth glass jars fitted with Teflon lined lids and filled with
Individual fullerene nanoparticles became slightly larger and
¼-strength-modified Hoagland solution (Ma and Burken,
the average size of fullerene nanoparticles was 61.4 þ 13.2 nm
2003). For each reactor, a cottonwood cutting was inserted
and 66.1 þ 12.5 nm in systems containing 2 and 15 mg/L ful-
through the hole in the center and a Teflon tube was inserted
lerene nanoparticles, respectively. The aggregation of nano-
through the other hole on the lid. The hole in the center with
particles could partially result from the coagulation and
plant cutting was sealed with Teflon tape and acrylic caulk, and
flocculation process as a result of double layer compression by
the plant cutting was positioned such that the cutting was about
ions in Hoagland solutions. Fullerene nanoparticles in plant
1 cm above the jar bottom. Evapotranspiration of Hoagland
treatments became slightly more angular and the surface was
solution was replenished as needed through the Teflon tube.
not as smooth as freshly prepared. Typical fullerene nano-
The jars were wrapped with aluminum foil to prevent algal
particles after sonication and after exposure to plants and TCE
growth. A similar configuration of the experimental setup can
are shown in Fig. 1. The transmission electron microscope
be found in literature (Burken and Schnoor, 1998).
image clearly indicated the attachment of certain materials on
After cuttings showed strong signs of sprouting and root
the surface of fullerene nanoparticles. The attachment could
development, Hoagland solutions were replaced with new
be microorganisms, TCE molecules, and/or water molecules.
solutions containing designated concentrations of fullerene
Exact composition of the attachment, however, needs further
nanoparticles. Afterward, 10 mL of TCE stock solution
investigation.
(450 mg/L) was added slowly through the feeding tube to
The addition of up to 15 mg/L of fullerene nanoparticles
obtain a final TCE concentration of 10 mg/L. The tube was
did not result in any significant differences in plant mor-
sealed immediately with Teflon tape after TCE feeding.
phology and water transpiration compared with reactors
Three or four replicates were prepared for each dosing sce-
containing 10 mg/L of TCE only. In reactors containing SON/
nario and the specific dosing scenarios were as follows:
nC60, TCE concentrations or mass in plant biomass positively
10 mg/L TCE only, 10 mg/L TCE þ 2 mg/L nC60, and 10 mg/
correlated with fullerene concentrations in solution, with
L TCE þ 15 mg/L nC60. The targeted fullerene concentrations
higher SON/nC60 resulting in more elevated TCE concen-
were obtained by diluting the stock solution with DI water,
tration or mass in plant tissues. Similar trend was observed in
assuming that the loss of fullerene in the synthetic process was
the growth media, with higher SON/nC60 resulting in higher
insignificant. Two viable cottonwood cuttings dosed with DI
TCE concentrations or mass in the Hoagland solution (Fig. 2).
water were used as controls. Two dead cuttings in the same
It is probable that C60 dispersed in water provided a new
setting were also included to account for water evaporation
phase of partitioning for TCE, rendering higher concentra-
from the reactors. The exposure lasted for 4 days and the
tions of TCE in solution. To evaluate whether elevated con-
feeding solution was not replenished during the experiment.
centration of TCE in plant tissues could be explained by
Transpiration ranged from 123.7 þ 10.3 mL for reactors with
increased concentration of TCE in solution, the ratio of TCE in
TCE only, 132.5 þ 28.7 mL for reactors with TCE þ 2 mg/L of
plant biomass and TCE in solution was calculated. The ratio
nC60, and 121.7 þ 17.6 mL for reactors with TCE þ 15 mg/L of
became higher with increasing concentrations of SON/nC60.
nC60, respectively.
Even though the differences between the ratios are statisti-
cally insignificant ( p ¼ 0.05), the steady trend may still indi-
Sample analysis
cate that the presence of SON/nC60 facilitated plant uptake of
At termination, plants were sacrificed and separated into TCE. Even though fullerene lacks the tubular structure of
different sections including roots, stems under the lid, stems CNTs to pierce through plant cells to facilitate contaminant
above the lid, and new stems and leaves. Plant tissues were uptake, the unique structures of fullerene probably make it
placed into 22-mL vials, which were immediately sealed with easier to be taken up by plants. Lin and colleagues (2009)
FULLERENE AFFECTS TRICHLOROETHYLENE UPTAKE BY PLANTS 991

FIG. 1. Representative SON/

nC60 fullerene nanoparticles of
(A) freshly synthesized, (B) ful-
lerene nanoparticles in systems
containing plants, 10 mg/L
TCE þ 2 mg/L fullerene particle,
and (C) fullerene nanoparticles in
systems containing plants,
10 mg/L TCE þ 15 mg/L fuller-
ene nanoparticles. Fullerene na-
noparticles were sampled at the
end of experiment. The bars
shown in the figure are 50 nm.
TCE, trichloroethylene.

demonstrated that nC70 aggregates with the size from 40 to uptake of TCE by plants. The fullerene nanoparticle aggre-
70 nm can be taken up by rice roots and transported to shoots gates were generally <70 nm.
and leaves through vascular tissues while CNT uptake was The concentration of TCE in different plant compartments
not observed. The same study also indicated that C70 in vas- (e.g., roots and stems) demonstrated similar trends as in
cular systems could leak into surrounding cells and intercel- whole plant seedlings in the presence of SON/nC60 (Fig. 3),
lular spaces. Uptake of fullerene nanoparticles laden with indicating that TCE-SON/nC60 complex was transported to
TCE on the surface may be a possible reason for enhanced all these compartments. Examination of the distribution of
TCE in plant compartments showed that SON/nC60 en-
hanced the accumulation of TCE in the stems below lid but
reduced the accumulation of TCE in other sections. The results
500 TCE in plant biomass 0.51 could be ascribed to (1) the enhanced adsorption of TCE-
450 0.5 fullerene complex on the surface of stems below lid and (2) the
TCE in solution
400 0.49
TCE in plant/TCE in
solution
d 0.48
350
Total TCE (ug)

0.47
300
c 40
Ratio

0.46 TCE only

250
c 0.45 35 T+F 2ppm
TCE dry biomass (ug/g)

200
b 0.44 30 T+F 15ppm
150 0.43
b 25
100 a 0.42
50 0.41 20
0 0.4 15
T T+F 2ppm T+F 15ppm
10
FIG. 2. TCE in plant biomass and in growth media 4 days 5
after plants were exposed to TCE and TCE þ SON/nC60 ful-
lerenes. Initial TCE concentration was 10 mg/L in all treat- 0
ments. Theoretical concentrations of fullerene nanoparticles TCE in roots TCE in SB TCE in SA TCE in NS
are 2 and 15 mg/L. The reported results are the average of
three or four replicates; error bars represent standard devia- FIG. 3. Average dry biomass concentration of TCE in dif-
tion. Bars with different letters are significantly different. Red ferent compartments of eastern cottonwood exposed to TCE
dots represent the ratio between the average TCE in plant or TCE þ SON/nC60. Error bars represent standard deviation.
biomass and TCE in solution. T, TCE; F, fullerene nano- n ¼ 3, 4. T, TCE; F, fullerene nanoparticles; SB, stems below the
particles. lid; SA, stems above the lid; NS, newly developed stems.
992 MA AND WANG

transport kinetics. It is likely that transport of fullerene-TCE implications, and the complex interactions between ENPs,
complex was faster in fresh roots than in stems. A previous plants, and contaminants warrant further investigation.
research indicated that transport of fullerene nanoparticles in
mature plants is relatively slow and fullerenes are predomi- Author Disclosure Statement
nant in and near the vascular tissues of plant stems (Lin et al.,
No competing financial interests exist.
2009).
Similar experiments were conducted with a bush plant,
Redosier dogwood, and the results were similar to what was References
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