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Grantee Research Project Results

Final Report: Environmental Transport, Biodegradation, and Bioaccumulation of Quantum Dots and Oxide Nanoparticles

EPA Grant Number: R833861
Title: Environmental Transport, Biodegradation, and Bioaccumulation of Quantum Dots and Oxide Nanoparticles
Investigators: Aga, Diana S. , Watson, David , Colon, Luis , Banerjee, Sarbajit
Institution: University of Buffalo
EPA Project Officer: Aja, Hayley
Project Period: July 1, 2008 through June 30, 2011
Project Amount: $400,000
RFA: Exploratory Research: Nanotechnology Research Grants Investigating Fate, Transport, Transformation, and Exposure of Engineered Nanomaterials: A Joint Research Solicitation - EPA, NSF, & DOE (2007) RFA Text |  Recipients Lists
Research Category: Nanotechnology , Safer Chemicals

Objective:

This research aimed to investigate the influence of size and surface chemistry of quantum dots (QDs) (i.e., CdS and CdSe) and engineered metal oxide (MO) nanomaterials (i.e. CeO2, HfO2, ZrO2, TiO2) on their environmental mobility, biodegradation, and bioaccumulation. The specific goals are to: (1) characterize the influence of natural organic matter (NOM) on the surface functionalization, solubility, and stability of QD and MO suspensions; (2) examine the effects of NOM on the transport behavior and degradation of various formulations of QD and MO in soil columns; and (3) measure the bioaccumulation of QD and MO as a function of size and NOM concentration in a model organism (Eisenia). We hypothesize that size, surface chemistry, bioavailability, and solubility of QD and MO are closely related parameters that affect the environmental fate and potential ecological impacts of QD and MO nanomaterials.

Summary/Accomplishments (Outputs/Outcomes):

The influence of natural organic matter (NOM) on the environmental behavior of engineered nanomaterials was investigated using CdSe quantum dots (QDs) and metal oxides (MO). We used the Suwannee River humic acid and fulvic acid standards (International Humic Substances Society) as model NOM to characterize the solubility, phase transfer and dissolution of QD and MO upon interaction with NOM. For non-aqueous nanoparticle suspensions, the NOM-nanomaterial interactions were examined using simple phase transfer experiments, which demonstrated that hydrophobic QD (CdSe QDs capped with trioctylphosphine oxide (TOPO), tetradecyl phosphonic acid (TDPA) or oleic acid (OA) in hexane suspensions can efficiently transfer into the aqueous phase in the presence of humic acids (HA) and fulvic acids (FA). Phase transfer proceeded for all QDs regardless of the surface-capping groups. No phase transfer was observed in the control set-ups where nanopure water was used. In the case of MO (HfO2-monoclinic, ZrO2-tetragonal and solid-solution HfxZr1-xO2-monoclinic and tetragonal MO capped with TOPO), some selectivity dependent on crystal structure was evident, only allowing phase transfer of particles with monoclinic structure. Although some transfer of monoclinic MO nanoparticles were detected in nanopure water, the MOs were only stabilized in the presence of NOM. Our experiments revealed that the nanoparticles were not completely degraded after phase transfer, but some leaching of the core metal was observed. Close interacting units of HA and QD/MO are evident from the TEM images, where the crystalline nanoparticles are agglomerated to amorphous HA/FA. QDs retained their optical absorption after phase transfer. The rate of phase transfer is influenced by pH, ionic strength and the levels of HA/FA in solution. This NOM-mediated phase transfer also has been demonstrated using two natural surface water samples.
 
Our phase transfer experiments also provided us a better understanding of the interactions between NOM and QD/MO. Two synergistic mechanisms can be deduced from our results: (1) hydrophobic interactions between non-polar functional groups of HA/FA and organic capping groups of QD/MO, and (2) displacement of capping groups by Lewis basic groups of HA/FA. The understanding of these mechanisms will be instrumental in predicting the fate and transport of these engineered nanomaterials. Our findings showing that even QD with hydrophobic surface capping can be potentially transported into the aquatic environments upon interaction with NOM is environmentally relevant. The NOM-mediated transfer of QD gave rise to decreased particle sizes and some leaching of Cd2+ into aqueous solution as verified by emission spectroscopy and by inductively couple plasma mass spectrometry analysis.
 
Soil column experiments were initiated using water-soluble suspensions of QD (CdSe QDs capped with cysteine (CYS) or mercaptopropionic acid (MPA) and core-shell CdSe/ZnS QD that is COOH terminated) in soil. Our study revealed that both water-soluble QD and free Cd2+ ions have negligible mobility in soil. However, when leached with a metal chelator such as EDTA, QD behaved differently from free Cd2+. EDTA enables the extraction of free Cd2+ (not QD bound) out of the soil column while majority of the QD remain sorbed on the top soil, even after more than 10 column volumes have been passed through the column. These results demonstrate effects of environmental chelators on the potential transport of nanomaterials that are otherwise immobile in soil.
 
We also investigated the potential uptake of water-dispersible CdSe/ZnS QD by Chara australis, a major component of many lake and stream ecosystems, and Arabidopsis thaliana, a commonly used model plant that develops and responds to stress in a manner typical for many plants. Live plant roots were imaged for intact QD by fluorescence microscopy, which revealed that most, if not all, of the QD can be found on the outside of the roots. The adsorbed QD were also visibly aggregated. Fluorescence microscopy images confirmed that the QD were not internalized, and were generally intact on the root surfaces. We similarly observed that QD adhered mainly to the external surface in Chara australis shoots and rhizoids. For plants exposed to QD, the concentrations of Cd and Se found in the roots were significantly different from the control. However, the levels of Cd in the roots of QD-treated plants were not significantly different from the Cd2+-treated plants. Unlike free ions, the amount of Cd and Se taken up from QD did not increase with time, suggesting that only adsorption to the root surface is occurring. The levels of Cd and Se in the leaves of QD-treated plants were not significantly different from the controls suggesting that QD were not translocated from the roots.

Finally, we investigated the bioaccumulation behavior of QD by Eisenia andrei earthworms in a terrestrial environment. Earthworms were exposed to QD-treated soil for up to 4 weeks and analyzed for cadmium and selenium concentration using inductively coupled plasma mass spectrometry. Results were compared with those from earthworms exposed to cadmium nitrate and selenious acid, as positive controls, and those exposed in untreated soil (negative control). Earthworms exposed to QD showed significant bioaccumulation of cadmium and selenium (5.3- and 1.5-fold higher concentration over negative controls, respectively) after 4 weeks. Over the same 4 weeks, positive control earthworms accumulated 9.2- and 2.2-fold higher cadmium and selenium, respectively, than negative controls for a much more substantial final body burden of the two elements. The concentrations also increased with exposure time, suggesting that further bioaccumulation may take place with even longer exposure time. The molar ratio of cadmium to selenium in the QD-exposed worms was closer to the ratios seen in positive control worms than to the pure QD. The results observed in this study indicate that QDs are taken up predominantly in the degraded form.

Conclusions:

In conclusion, our studies suggest that chemical modification of QD to protect them from environmental degradation could potentially reduce accumulation of the nanoparticles by earthworms, and potentially by other soil biota. Plant uptake experiments also suggest that QD is not translocated from roots to other parts of the plant. Results from this study suggest that the potential deleterious effects of QD, MO, and perhaps other engineered nanomaterials may be reduced if the surface coatings are made stable, protecting the release of heavy metals into the environment. Finally, results from the phase-transfer experiments revealed that NOM and other chelating agents in the environment could provide a means by which hydrophobic nanoparticles can enter the aquatic environment, and release toxic elements such as Cd2+ and/or Se2-. These studies demonstrate the importance of having stable surface capping ligands on the surfaces of engineered nanoparticles to reduce their potential negative impacts once they are released into the environment.


Journal Articles on this Report : 10 Displayed | Download in RIS Format

Publications Views
Other project views: All 36 publications 10 publications in selected types All 10 journal articles
Publications
Type Citation Project Document Sources
Journal Article Akaighe N, MacCuspie RI, Navarro DA, Aga DS, Banerjee S, Sohn M, Sharma VK. Humic acid-induced silver nanoparticle formation under environmentally relevant conditions. Environmental Science & Technology 2011;45(9):3895-3901. R833861 (Final)
  • Abstract from PubMed
  • Abstract: ACS Publications-Abstract
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  • Journal Article Celiz MD, Colon LA, Watson DF, Aga DS. Study on the effects of humic and fulvic acids on quantum dot nanoparticles using capillary electrophoresis with laser-induced fluorescence detection. Environmental Science & Technology 2011;45(7):2917-2924. R833861 (Final)
  • Abstract from PubMed
  • Abstract: ACS Publications-Abstract
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  • Journal Article Depner SW, Kort KR, Banerjee S. Precursor control of crystal structure and stoichiometry in twin metal oxide nanocrystals. CrystEngComm 2009;11(5):841-846. R833861 (2009)
    R833861 (Final)
  • Abstract: CrystEngComm-Abstract
    Exit
  • Journal Article Navarro DA, Watson DF, Aga DS, Banerjee S. Natural organic matter-mediated phase transfer of quantum dots in the aquatic environment. Environmental Science & Technology 2009;43(3):677-682. R833861 (2009)
    R833861 (Final)
  • Abstract from PubMed
  • Abstract: ACS Publications-Abstract
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  • Journal Article Navarro DA, Banerjee S, Aga DS, Watson DF. Partitioning of hydrophobic CdSe quantum dots into aqueous dispersions of humic substances: influence of capping-group functionality on the phase-transfer mechanism. Journal of Colloid and Interface Science 2010;348(1):119-128. R833861 (Final)
  • Abstract from PubMed
  • Full-text: ScienceDirect-Full Text HTML
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  • Abstract: ScienceDirect
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  • Other: ScienceDirect-PDF
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  • Journal Article Navarro DA, Banerjee S, Watson DF, Aga DS. Differences in soil mobility and degradability between water-dispersible CdSe and CdSe/ZnS quantum dots. Environmental Science & Technology 2011;45(15):6343-6349. R833861 (Final)
  • Abstract from PubMed
  • Abstract: ACS Publications-Abstract
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  • Journal Article Navarro DA, Depner SW, Watson DF, Aga DS, Banerjee S. Partitioning behavior and stabilization of hydrophobically coated HfO2, ZrO2 and HfxZr1-xO2 nanoparticles with natural organic matter reveal differences dependent on crystal structure. Journal of Hazardous Materials 2011;196:302-310. R833861 (Final)
  • Abstract from PubMed
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  • Abstract: ScienceDirect
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  • Journal Article Navarro DA, Bisson MA, Aga DS. Investigating uptake of water-dispersible CdSe/ZnS quantum dot nanoparticles by Arabidopsis thaliana plants. Journal of Hazardous Materials 2012;211-212:427-435. R833861 (Final)
  • Abstract from PubMed
  • Full-text: ScienceDirect-Full Text HTML
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  • Other: ScienceDirect-PDF
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  • Journal Article Stewart DT, Noguera-Oviedo K, Lee V, Banerjee S, Watson DF, Aga DS. Quantum dots exhibit less bioaccumulation than free cadmium and selenium in the earthworm Eisenia andrei. Environmental Toxicology and Chemistry 2013;32(6):1288-1294. R833861 (Final)
  • Abstract from PubMed
  • Abstract: Wiley Online-Abstract
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  • Journal Article Stewart DTR, Celiz MD, Vicente G, Colon LA, Aga DS. Potential use of capillary zone electrophoresis in size characterization of quantum dots for environmental studies. TrAC Trends in Analytical Chemistry 2011;30(1):113-122. R833861 (Final)
  • Full-text: ScienceDirect-Full Text HTML
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  • Abstract: ScienceDirect
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  • Supplemental Keywords:

    bioavailability, soil contamination, UV, IR Raman, Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy, laser-induced fluorescence, heavy metals, capillary zone electrophoresis, Health, Scientific Discipline, Health Risk Assessment, Risk Assessments, bioavailability, nanomaterials, manufactured nanomaterials, ecological risk assessment, biogeochemistry, biological pathways, bioaccumulation, nanotechnology, nanochemistry, nanoparticle toxicity, quantum dots, cellular response to nanoparticles, toxicologic assessment, quantification of non-cancer risk, biochemical research

    Progress and Final Reports:

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    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Conclusions drawn by the principal investigators have not been reviewed by the Agency.

    Project Research Results

    • 2010
    • 2009 Progress Report
    • Original Abstract
    36 publications for this project
    10 journal articles for this project

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