The analysis of Metal-containing Engineered Nanoparticles
Transcript of The analysis of Metal-containing Engineered Nanoparticles
Spiros A. Pergantis
Environmental Chemical Processes Laboratory,
Dept. of Chemistry, University of Crete
Voutes Campus, Heraklion, 70013, Greece
The analysis of Metal-containing Engineered Nanoparticles
using SINGLE PARTICLE ICP-MS
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Presentation Outline
• Brief intro to sp ICP-MS
• Application of sp ICP-MS for Ag NP detection in a marine mesocosm experiment
• Limitations of sp ICP-MS
• NP Sizing using HDC, FFF, and ion mobility with sp ICP-MS
• NP characterization using modified sp ICP-MS approaches
• Development and application of single cell ICP-MS analysis
Inductively Coupled Plasma – Mass Spectrometry (ICP-MS)
• Analysis of sample with a heavy or complex matrix (i.e. seawater, biological samples)
• Routine analysis for screening purposes (high throughput with minimum sample preparation)
• Not labor intensive
• Sensitive with LOD adequate for realistic environmental concentrations
Inductively Coupled Plasma – Mass Spectrometry (ICP-MS)
Liquid sample
Single Particle (SP) - ICP-MS
Au+
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Single Particle ICP-MS of a Au NP suspension
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Degueldre, C.; Favarger, P. Y.; Wold, S. Anal. Chim. Acta 2006, 555, 263-268.
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Particle Size Distribution
𝑑𝑖,𝐴𝑔𝑁𝑃 =3 6𝑚𝑖,𝐴𝑔𝑁𝑃
𝜋 𝜌
Anastasia Tsiola 1,2, Paraskevi Pitta 2, Margarita Kagiorgi 2, Ioanna Kalantzi 2,
Kyriaki Mylona 2,3, Stella Psarra 2, Ioulia Santi 1,2, Claudio Toncelli 2,3,
Spiros A. Pergantis 3, Manolis Tsapakis 2
1 University of Crete, Department of Biology2 Hellenic Centre for Marine Research, Institute of Oceanography
3 University of Crete, Department of Chemistry
Effects of silver nanoparticle exposure at the ng L-1 level
on marine microbial plankton dynamics
Background
engineered NPs are used in a wide range of applications
AgNPs release in coastal zone is expected to increase in the near future
consequences on aquatic biota have been already determined
apoptosis
ROS production
decreased viability and growth rates
decreased chlorophyll content
alterations in community composition
alterations in protein expression patterns
Silver nanoparticles of 60 nm diameter (TEM; Nanoxact,
No MRL1009)
Background
unrealistic and simplified conditions
high concentrations of AgNPs
single-species cultures or pre-treated estuarine & freshwater
communities
short-term experiments
Aim – AQUA-NANO project
potential effects of AgNPs in a natural planktonic communityno pre-filtration step, total marine plankton incubated
environmental relevant concentrations of AgNPs100-1000 ng Ag L-1
long-term effectsover a month
interaction effects on the genus or species level, when possible
considering the ambient physico-chemical parameters
Methodology
Analytical challenges – FI sp ICP MS
very dilute samples
very complex matrix
large number of samples
Whole-community approach challenges – mesocosms
microbial planktonic members present
constant interplay with highly-variable ambient conditions (pH,
temperature, organic matter, O2 and others)
single particle Inductively Coupled Plasma Mass Spectrometry
Ar gas
3-5 mmdilution zone
HPLC pump
Injector (20 μL loop)
di water
10-50 μL min-1
0.8 mL min-1
Fused silica capillary
Toncelli et al., 2016
Methodology
Analytical challenges
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Methodology
Analytical challenges
AgBPEI 60 nm NPs at a concentration of 200 ng Ag L-1. Histogram is the sum of 3 injections.
dH2O seawater
𝑚𝐴𝑔𝑁𝑃𝑠𝑡𝑑 = 𝑘. ത𝑞𝐴𝑔𝑁𝑃
𝑘 =𝑚𝐴𝑔𝑁𝑃
𝑠𝑡𝑑
ത𝑞𝐴𝑔𝑁𝑃
𝑚𝑖,𝐴𝑔𝑁𝑃 = 𝑘. 𝑞𝑖,𝐴𝑔𝑁𝑃
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𝑚n,𝐴𝑔𝑁𝑃 = 𝑘. 𝑞n,𝐴𝑔𝑁𝑃
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Std AgNP 60 nm
ത𝑞𝐴𝑔𝑁𝑃
𝑑𝑖,𝐴𝑔𝑁𝑃 =3 6𝑚𝑖,𝐴𝑔𝑁𝑃
𝜋 𝜌
ҧ𝑑𝐴𝑔𝑁𝑃
𝜀𝑛 =𝑛𝑑𝑒𝑡𝑛𝑖𝑛𝑗
NP number concentration determination
Part of the “Aqua-Nano” project ( http://aqua-nano.hcmr.gr/ )
poly(vinylpyrrolidone), PVP (Branched poly(ethylenimine)), BPEI
AgPVP AgBPEI
40 nm
60 nm
Control
200 ppt Ag for each Ag NP type
15 tanks in total
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Methodology
Whole-community approach challenges
Mesocosm experiment “Cretacosmos- HCMR”
3-m3 incubations, 3 replicates
33 days
biotic and abiotic factors studied
Mesocosm experiment
Microcosm experiments (Toncelli et al., 2017 and Tsiola et al., 2017)
coastal seawater from the Cretan Sea, April-May 2015
branched poly(ethyleneimine) AgNPs, 60 nm
100 ng Ag L-1 spiking concentration per day for 10 days (step-wise)
final maximum concentration: 1000 ng Ag L-1
3x BPEI of 60 nm diameter
3x controls (C)
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Temporal changes in Plankton abundances
Cyanobacterial growth
was inhibited
• The amount of a lysogeny-related gene increased and viral auxiliary metabolic
genes that are involved in cyanobacterial photosynthesis decreased, revealing a
damaged photosynthetic potential after AgNP exposure.
• Microbial plankton was significantly affected due to both increased dissolved silver
ions and decreased AgNP size.
• The presence of AgNPs alters the functioning of the marine food web by hampering
important viral and bacterial processes.
General Conclusions
Environ. Sci.: Nano, 2018,5, 1965-1980