FATE OF COATED NANOPARTICLES IN LANDFILL LEACHATE Bolyard.pdf · 2012. 12. 15. · FATE OF COATED...
Transcript of FATE OF COATED NANOPARTICLES IN LANDFILL LEACHATE Bolyard.pdf · 2012. 12. 15. · FATE OF COATED...
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FATE OF COATED NANOPARTICLES IN
LANDFILL LEACHATE
University of Central Florida
Stephanie C. Bolyard, EPI Debra R. Reinhart, PhD, PE, BCEE Swadeshmukul Santra, PhD
Graduate Research Assistant Assistant VP of Research Associate Professor
Civil, Environmental, and
Construction Engineering
Office of Research and
Commercialization
Nanoscience Technology
Center
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Introduction
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Project Objectives
This research seeks to understand the fate of NMs
within waste environments by examining the interactions
between NPs and landfill leachate components.
Primary focus was on the effect of Zinc Oxide (ZnO),
Titanium Dioxide (TiO2), and Silver NPs (Ag) on:
• Biological landfill processes
• Solids aggregation
• Chemical speciation of dissolved metals in leachate
following the addition of nanoparticles (NPs)
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Methodology
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Leachate Collection and Chemical
Characterization
Middle-aged and mature leachate samples were collected and
characterized from MSW landfills in Florida.
All leachate samples were characterized for:
• pH
• Chemical and biochemical oxygen demand
• Ammonia-nitrogen
• Conductivity
• Alkalinity
• Heavy metals
• Total suspended and dissolved solids
• Dissolved humic acid concentration
All procedures followed Standard Methods for the Examination of
Water and Wastewater.
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Materials Used
Coated Zinc Oxide (ZnO).
Triethoxycaprylylsilane
Coated Titanium Dioxide (TiO2).
Hydrated Silica and
Dimethicone/Methicone Copolymer
and Aluminum Hydroxide.
Coated Silver (Ag).
Polyvinylpyrrolidone (PVP) coated Ag
nanoparticles
Per
cent
Dis
trib
uti
on
Average Particle
Distribution: 149 nm
DLS of ZnO NPs
ZnO NPs
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Leachate Exposed to Coated NPs
Leachate was exposed to varying
concentrations of coated NPs.
• 100 µg/L NPs
• 1.0 mg/L NPs
• 100 mg/L NPs
Continuously stirred (~24°C)
Control reactor was treated in the
identical manner without NPs.
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Materials Characterizations
HRTEM: Particle size, crystallinity and particle morphology,
HRTEM - Selected Area Electron Diffraction (SAED) for identification
of crystallinity and elemental analysis (composition)
DLS to understand size and size distribution of the particles in solution,
UV-Vis spectroscopy for absorption measurements.
Fluorescence spectroscopy for detailed investigation of the emission
properties of coated ZnO particles and for understanding their
interaction with leachate components,
FT-IR spectroscopy for understanding the interaction of coated ZnO
NPs with the leachate components,
AFM for the imaging of ZnO NPs in leachate components.
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Effect of Coated NPs on Biological
Processes
Biochemical Oxygen Demand (BOD5) was performed
following standard methods 5120B.
Biochemical Methane Potential (BMP) was performed
following ASTM method E2170.
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Size Fractionation of Leachate Samples
Exposed to Coated NPs
Size fractionation was used to determine the effect of solids
aggregation on the fate of NPs and to quantify the
concentration of dissolved metal ions in each fraction.
1.0-nm (1000 NWML regenerated cellulose) filter.
Concentration of metals (Zn, Ag, Ti) in each size fraction was
quantified using Inductively Coupled Plasma-Optical Emission
Spectrum.
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Chemical Speciation of Dissolved
Metals using Visual MINTEQ
Chemical speciation of metals in leachate is an important
component in understanding the toxicity, mobility, and
bioavailability of these metals in the environment.
Estimate the chemical species and equilibrium mass distribution
of dissolved metals found in leachate using Visual MINTEQ
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Findings
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NP Dispersibility
Humic acids (HA) greatly increased
the dispersibility of the coated ZnO
NPs, which can be attributed to
over-coating of NP surface by HA
through hydrophobic-hydrophobic
interaction.
Fourier Transform Infrared (FT-IR)
spectroscopy and fluorescence
characterization data confirmed
that HA was adsorbed onto coated
ZnO NPs, increasing their
wettability.
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NP Interaction with Humic Acids
High Resolution Transmission Electron Microscopy images
suggested that ZnO NPs were embedded in leachate
matrices after addition to leachate samples. TiO2 was
observed embedded in purchased HA.
TiO2 TiO2/HA
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NP Agglomeration in Leachate
Dynamic Light Scattering and Atomic Force Microscopy
data revealed that dispersed ZnO NPs tended to
agglomerate in leachate. Fractionation studies also
showed that ZnO as well as Ag NPs agglomerated in
leachate.
Humic Acid Humic Acid/ZnO
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Agglomeration of ZnO-HA Composite
and De-Agglomeration Upon Dilution
De-agglomeration of ZnO-HA composite upon
dilution
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NP Dissociation in Leachate
An increase in the dissolved concentration of all tested NPs
was observed in some leachates, which supports dissociation
of these NPs, however this fate accounted for less than 1% of
the mass of NP added.
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Biological Effects
ZnO, Ag, and TiO2 NPs did not affect biological
processes when added to middle-aged and mature
leachate as measured by Biochemical Oxygen Demand
and Biological Methane Production tests.
1
10
100
1000
0 20 40 60 80 100 120
BO
D (
mg
/L)
Time (Days)
Biochemical Oxygen Demand Over Time
(Leachate B)
Control 100 ug/L 1.0 mg/L 100 mg/L
0
5
10
15
20
25
0 10 20 30 40 50 60
Ga
s P
rod
uct
ion
(m
L)
Time (Days)
Cumulative Gas Production
(Leachate B)
Control 100 ug/L ZnO 1 mg/L ZnO 100 mg/L ZnO
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Metal Speciation Modeling
MINTEQ models showed that dissolved Zn, Ag, and Ti in
leachate were associated with HA, NH3/Cl, and hydroxide,
respectively. Low concentrations of free ions were
predicted.
0.001 0.01 0.1 1 10 100
Day 0
Day 7
Day 30
Concentration (µg/L)
Da
y
Chemical Speciation of Silver in Leachate E
Ag+1 AgCl (aq) AgCl2- AgCl3-2 AgNH3+ Ag(NH3)2+
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Conclusions
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Conclusions: Summary
Insight into the mobility of NPs in landfills
• Aggregation may prevent movement through traditional containment
systems
• Transported out of the landfill in leachate due to increased dispersability
Absence of inhibitory effects on landfill processes
• Biological treatment of leachate should be unaffected by the presence of
NPs
• Bioavailability of dissolved metals was not affected by the added NPs
due to the affinity of dissolved metals for DOM (HA), NH3/Cl, and
hydroxide.
Challenging to predict overall mobility of NMs in a landfill due to the
complexity of landfill leachate and the utilization of different NM
coatings.
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Questions
? Debra Reinhart, PhD, PE, BCEE
Stephanie C. Bolyard, EPI
Swadesh Santra, PhD