Nanomatriaux et nanoparticules manufactures : Risques - - PowerPoint PPT Presentation
Nanomatriaux et nanoparticules manufactures : Risques environnementaux / Jean Yves Bottero, and Mlanie Auffan, Jrme Rose, Cline Botta, Jrme Labille, Armand Masion, N Solovitch Vella, E.M Hotze And the US and French members
Jean‐Yves Bottero, and Mélanie Auffan, Jérôme Rose, Céline Botta, Jérôme Labille, Armand Masion, N Solovitch‐Vella, E.M Hotze And the US and French members
for the Environmental Implications of Nano Technology
IRSN 21 Septembre 2010
Quelques chiffres: Nombre de produits répertoriés en 2009
Source: Program Emerging Nanotechnology
En 2010: plus de 2000
Source Nanowerk
Catégories
Dans le domaine dit « du bien être »
From Ch Robichaud PhD DUKE Univ Decembre 2010
Les éléments les plus présents
Understanding AgNPs formation/ transformation in wastewater treatment
Sludge ID 68349 (from Midwest region) Elemental Analysis Element (mg kg-1) Mg 13500 Ag 856 Mn 1070 Al 57300 Na 6080 Ca 98900 P 57200 Cu 1720 Ti 4510 Fe 51000 Zn 1530
Blaser, S. A. et al., Science of the Total Environment (2008).
Targeted National Sewage sludge Survey Statistical Analysis Report (Released in Jan 2009)
74 plants across the States Total metal contents Pharmaceuticals, steroids, and hormones
1
Tout n’est pas NANO !
NP < 30 nm méritent une considération spéciale en écotoxicité… 30 nm M.Auffan et al., NATURE nano, 09- 2009 Strong increase
surface atom number Strong surface reactivity < 30 nm
Transformation?
http://www.pearsonsuccessnet.com/iText/products/0‐13‐115075‐8/text/chapter36/concept36.1.html
Producers Flowers Phytoplancton bacterias.. Primary consumers Grasshoper Zooplancton Secondary consumers Mouse Herring Tertiary consumers Snake Cod Quaternary consumers Hawk Killer whale A terrestrial food chain A marine food chain
I
i c s t r e n g t h p H
Inorganic colloïds
Biofilms
diffusion
Organic molecules pollutants
A-Transformation from products: speciation, surface properties and stability
A- Transformation Ex 1:Fate
in water from hydrophobic to hydrophilic material
stirring
stable dispersion of nanometric crystallites (nC60)
u l t r a c e n t r i f u g a t i
multi‐layer adsorption of H2 O irreversible modification of the surface gravimetric measurement
O vapour adsorption
at 30°C, and ambient pressure Previous
(110°C, 18h)
1 2 3 4 5 6 7 8 9 10 0.2 0.4 0.6 0.8 1 P (H2O) / P0 number of H2O monolayers adsorbed
Brant et al., 2007 JCIS Labille et al., 2006 Fullerenes Nanotubes and Carbon Nanostructures Labile et al., 2009, Langmuir, in press
stirring
C60 fullerite
H2 O
4000 3000 2000 1000 0.0 0.2 0.4 0.6 Absorbance Wave number (cm
nC60 pure C60
C‐OH H2O
FTIR
2 4 6 8 10 12 14
ppm C60 AQU/nC60 fullerol
1H SS NMR
CO‐H H2O hydroxylation of the nC60 surface gives hydrophilic surface
Labille et al., langmuir, in press 2009
J Labille et al (Env Pollution) 2010 and M Auffan et al, ES and T et al, ES and T 2010
Si O CH3 CH3
n
UV alteration of PDMS coating ?
Sand Sand and FeOOH
Shihong Lin et al , Duke N Solovitch et al, Environmental Science And Technology 2010
0.1 0.2 0.3 0.4 0.5 0.6 1.E-04 1.E-03 1.E-02 1.E-01 1.E+00 salt concentration (mol/L) attachment coefficient NaCl CaCl2 NaCl + gellan NaCl + A. tannic
no surface charge favours aggregation
stabilisation aggregation
ionic strength pH
bio‐ available not bio‐ available
electrostatic or sterric repulsions favour dispersion
Coating is often used by suppliers to improve NP dispersion, but is rarely specified.
In water :
stable NPs
t ~ 1s
In medium :
unstable NPs = adsorption + aggregation
Initial conditions: 3 mg/l NPs 108 cells/ml
Zeyons et al, ES and T 2009
Zeyon, Thill et al
Zeyon, Thill et a ES and T 2008 et Langmuir 2009
M.Auffan et al, ES and T 2006; M Auffan et al, Nanotoxicology 2009
Adapted from A Nel UCLA 2009
Transformation?
http://www.pearsonsuccessnet.com/iText/products/0‐13‐115075‐8/text/chapter36/concept36.1.html
Producers Flowers Phytoplancton bacterias.. Primary consumers Grasshoper Zooplancton Secondary consumers Mouse Herring Tertiary consumers Snake Cod Quaternary consumers Hawk Killer whale A terrestrial food chain A marine food chain Majorité des travaux
Membrane Integrity
test Rouge neutre
mitochondrial activity
WST1 test
Chromosomes
Micronuclei tests
ADN
comets tests
stress
Anti‐oxydants, mutant strains
Génotoxicity
ROS detection ROS Internalisation
TEM; Micro‐fluorescence..
synchrotron Cristalline Defects
TEM, Diffraction
Surface Spéciation and reactivity
EXAFS, XANES, RMN, FTIR
ROS production
O2
‐, O2
Cytotoxicity
Dissolution/aggregation
Cellules Eucaryotes
Nano‐γFe2 O3 enrobées Nano‐CeO2 50‐100 nm 2.5‐3 μm
Toxique Cellules Eucaryotes Non toxique
CeO2 7nm Fe0 < 20nm E.coli E.coli No cytotoxicity
Cytotoxicity ≤ 10 mg/L Cytotoxic > 70 mg/L No cytotoxic
γFe2O3 6nm E.coli
Damage membrane
30% of Ce(IV) ‐> Ce(III) on the surface of Cerine Oxydation of Fe° Dissolution / precipitation No structiural modification Toxicity is associated to the chemical instability of NP
Stress oxydatif through ROS production
Redox cycle (Ce3+/Ce4+) Fenton Reaction (Fe2+) e‐,ROS production
Ce4+ Ce3+
γFeOOH Fe3 O4
γFe2
3+O3
Fe0 Fe2+, ROS
stable
Zeyons et al, ES and T 2008; M Auffan et al, Nanotoxicology 2009
micronoyaux
control 0,06 mg/L 60 mg/L
Reduction of Ce(IV) in Ce(III)
No cytotoxic effects but … … génotoxicity at very low concentrations > 0,06 mg/L
ADN and chromosomic Damages
e‐,ROS
Ce4+ Ce3+ Stress oxydatif
CeO2 7nm
Xanes at L3 edge of Ce = 30% of reduced surface atoms M.Auffan et al, ES and T 2006; M Auffan et al, Nanotoxicology 2009
http://www.pearsonsuccessnet.com/iText/products/0‐13‐115075‐8/text/chapter36/concept36.1.html
Producers Flowers Phytoplancton bacterias.. Primary consumers Grasshoper Zooplancton Secondary consumers Mouse Herring Tertiary consumers Snake Cod Quaternary consumers Hawk Killer whale A terrestrial food chain A marine food chain Travaux qui se développent: cf I‐CEINT = mésocosmes
Ag0 PVP coated Nano‐Ag0
Caenorhabditis Caenorhabditis elegans elegans
Toxicity of coated‐silver nanoparticles : C.elegans 21 ± 17 nm
Wild and transgenic strains Mtl2: deficient in protein involved in metal regulation and detoxification
M Auffan In collaboration with J. Meyer (DUKE university, USA)
Dissolved Ag effect Toxicity of coated‐silver nanoparticles : C.elegans
PVP‐nanoAg
Wild Mtl2
24h 48h 72h 24h 48h 72h
Mtl2 strain more sensitive than the wild
In collaboration with J. Meyer (DUKE university, USA)
Fundulus heteroclitus Simulated silver speciation Assessing toxicity across a salinity gradient
Sea Water Low Salt
Tolerate Tolerate Tolerate Tolerate
In collaboration with C. Matson, R. Digiulio (DUKE university, USA)
Toxicity across a salinity gradient : Fundulus heteroclitus PVP coated nanoAg0 Gum Arabic coated nanoAg0 21 ± 17 nm 7 ± 3 nm
In collaboration with C. Matson, R. Digiulio (DUKE university, USA)
Toxicity across a salinity gradient
Embryotoxicity of PVP‐nanoAg0: ‘V‐curve’ shape Amount of dissolved Ag after interaction with the embryo Embryotoxicity: GumArabic‐nanoAg0 > PVP‐nanoAg0
Match Match
14‐20nm TiO2
Al(OH)3 thin amorphous layer improve PDMS coating protection against TiO2 photocatalytic effects PDMS = polydimethylsiloxane Al(OH)3 PDMS = polydimethylsiloxane hydrophobic properties enhance dispersion of the nanomaterial
CH3 CH3 Si O n
1O2
, O2
‐, OH
Hydrophobic surface Hydrophilic surface
UV, stirring, water
UV/Vis
X-Ray beam size: 10 mm X-Ray source: Rh X-Ray tube voltage: 30 kV Counting time: 9x360
Titanium map CCD Camera
Adsorption of Ti on algae
CCD image Adults Daphnia 9d exposure Concentration: 10 mg/l Calcium map Titanium map Combined map
XGT5000 Horiba Jobin Yvon X-Ray beam size: 10 mm X-Ray source: Rh X-Ray tube voltage: 30 kV Counting time: 20x360
100% hatching at 3 days post fertilization in contaminated media Living larvae
Days of exposure (post fertilization) % hatching
Danio rerio embryos hatching time
For all tested concentrations: significant effect on survival time survival time/control /control
First mortalities observed in contaminated solutions from 8d contact tact
Days of exposure % of alive larvae
Danio rerio larvae survival time
M Auffan et al, Nature Nano 09‐2009
If the mechanisms of the toxicity must be studied on « laboratory » NP, the researches must focused also on engineered products containing NP knowing that the formulations are complexe. As the studies on the ecosystems are at the beginning we need to coordinate the researches at the national level to have a systemic approach allowing to assess the toxicity in food webs and Prioritize in vivo testing at increasing trophic levels Try to be predicitive from the: ‐ knowledge and modelling of the interaction mechanisms of « nano » with water, components, biota ‐Modelling of the kinetic nteractions of NP in the aqueous media (water molecules, solutes, aggregation …… Study the interactions with biota within mesocosms managed by competent people and gathering the best labs around them.
http://www.pearsonsuccessnet.com/iText/products/0‐13‐115075‐8/text/chapter36/concept36.1.html
Producers Flowers Phytoplancton bacterias.. Primary consumers Grasshoper Zooplancton Secondary consumers Mouse Herring Tertiary consumers Snake Cod Quaternary consumers Hawk Killer whale A terrestrial food chain A marine food chain
Thanks to the french partners in I‐CEINT and particularly to: C Chanéac; J.P Jolivet; A Thill; A Botta, J.L Hazeman, O Proux…. And all the partners from CIRIMAT (Toulouse), ECOLAB (Toulouse) , HYGHES 5starsbourg), LCBM (Grenoble), , LBME (Marseille); LIEBE (Metz); IMEP (Marseille); IBEB (Cadarache) Inst Neel (Grenoble); ESRF (Fame beam line) Thanks to CNRS and CEA And also thanks to the american partners in I‐CEINT: M.R Wiesner (Duke); G Lowry (Carnegie‐Mellon); P Bertsch (Kentuky University); G Brown (Stanford); P Vikesland ……and many