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Al-Kattan A.,Empa - Swiss Federal Laboratories for Materials Science and Technology | Wichser A.,Empa - Swiss Federal Laboratories for Materials Science and Technology | Zuin S.,Venice Research Consortium | Arroyo Y.,Empa - Swiss Federal Laboratories for Materials Science and Technology | And 3 more authors.
Environmental Science and Technology | Year: 2014

In the assessment of the fate and effects of engineered nanomaterials (ENM), the current focus is on studying the pristine, unaltered materials. However, ENM are incorporated into products and are released over the whole product life cycle, though mainly during the use and disposal phases. So far, released ENMs have only been characterized to a limited extent and almost nothing is known about the behavior of these materials under natural conditions. In this work we obtained material that was released from aged paint containing nano-TiO2, characterized the particulate materials, and studied their colloidal stability in media with different pH and ionic composition. A stable suspension was obtained from aged paint powder by gentle shaking in water, producing a dilute suspension of 580 μg/L TiO2 with an average particle size of 200-300 nm. Most particles in this suspension were small pieces of paint matrix that also contained nano-TiO2. Some free nano-TiO2 particles were observed by electron microscopy, but the majority was enclosed by the organic paint binder. The pristine nano-TiO 2 showed the expected colloidal behavior with increasing stability with increasing pH and strong agglomeration above the isoelectric point and settling in the presence of Ca. The released TiO2 showed very small variations in particle size, Χ potential, and colloidal stability, even in the presence of 3 mM Ca. The results show that the behavior of released ENM may not necessarily be predicted by studying the pristine materials. Additionally, effect studies need to focus more on the particles that are actually released as we can expect that the toxic effect will also be markedly different between pristine and product released materials. © 2014 American Chemical Society.


Smulders S.,Catholic University of Leuven | Kaiser J.-P.,Empa - Swiss Federal Laboratories for Materials Science and Technology | Zuin S.,Venice Research Consortium | Van Landuyt K.L.,Catholic University of Leuven | And 4 more authors.
Particle and Fibre Toxicology | Year: 2012

Background: Nanomaterials can be contaminated with endotoxin (lipopolysaccharides, LPS) during production or handling. In this study, we searched for a convenient in vitro method to evaluate endotoxin contamination in nanoparticle samples. We assessed the reliability of the commonly used limulus amebocyte lysate (LAL) assay and an alternative method based on toll-like receptor (TLR) 4 reporter cells when applied with particles (TiO2, Ag, CaCO3 and SiO2), or after extraction of the endotoxin as described in the ISO norm 29701.Results: Our results indicate that the gel clot LAL assay is easily disturbed in the presence of nanoparticles; and that the endotoxin extraction protocol is not suitable at high particle concentrations. The chromogenic-based LAL endotoxin detection systems (chromogenic LAL assay and Endosafe-PTS), and the TLR4 reporter cells were not significantly perturbed.Conclusion: We demonstrated that nanoparticles can interfere with endotoxin detection systems indicating that a convenient test method must be chosen before assessing endotoxin contamination in nanoparticle samples. © 2012 Smulders et al.; licensee BioMed Central Ltd.


Zuin S.,Venice Research Consortium | Gaiani M.,Venice Research Consortium | Ferrari A.,GFC Chimica S.r.l. | Golanski L.,CEA Grenoble
Journal of Nanoparticle Research | Year: 2014

In this study we investigated the release of titanium dioxide (TiO 2), silver (Ag) and silica (SiO2) engineered nanoparticles (ENPs) from three different paints by using standardized water immersion test for coatings. Fibre-cement panels were coated with paints containing ENPs and then exposed to UV light and abraded to simulate weathering. After the static water immersion test, we observed a very low release of Ti (4-8 μg/l), while the Ag measured in leachates was under detection limit (0.1 μg/l). A small release of Si was measured in leachates, with 73 mg/l of Si released from paints containing SiO2 ENPs after 120 h of water immersion. The cumulative loss of Si was about 1.8 % with respect to initial amount of Si in paint. Microscopic results highlighted that SiO2 ENPs are mainly released in form of agglomerates with other particles, and only very few single SiO 2 ENPs were found in leachates. The results confirmed that Si migration is related to immersion cycles (wetting and drying cycles) of tested paints. © 2013 Springer Science+Business Media Dordrecht.


Al-Kattan A.,Empa - Swiss Federal Laboratories for Materials Science and Technology | Wichser A.,Empa - Swiss Federal Laboratories for Materials Science and Technology | Vonbank R.,Empa - Swiss Federal Laboratories for Materials Science and Technology | Brunner S.,Empa - Swiss Federal Laboratories for Materials Science and Technology | And 5 more authors.
Chemosphere | Year: 2015

In order to assess the possible risks of applications containing engineered nanomaterials, it is essential to generate more data about their release and exposure, so far largely overlooked areas of research. The aim of this work was to study the characterization of the materials released from paint containing nano-SiO2 during weathering and exposure to water. Panels coated with nano-SiO2 containing paint and a nano-free reference paint were exposed to accelerated weathering cycles in a climate chamber. The total release of 89 six-hour cycles of UV-illumination and precipitation was 2.3% of the total SiO2 contained in the paint. Additional tests with powdered and aged paint showed that the majority of the released Si was present in dissolved form and that only a small percentage was present in particulate and nano-particulate form. TEM imaging of the leachates indicated that the majority of the particulate Si was contained in composites together with Ca, representing the paint matrix, and only few single dispersed SiO2-NPs were detected. The results suggest that toxicological and ecotoxicological studies need to consider that the released particles may have been transformed or are embedded in a matrix. © 2014 Elsevier Ltd.


Zuin S.,Venice Research Consortium | Massari A.,Venice Research Consortium | Ferrari A.,GFC Chimica Srl | Golanski L.,CEA Grenoble
Science of the Total Environment | Year: 2014

Waterborne paints with integrated nanoparticles have been recently introduced into the market as nanoparticles offer improved or novel functionalities to paints. However, the release of nanoparticles during the life cycle of nano-enhanced paint has only been studied to a very limited extent. The paint composition could determine in what quantities and forms the nanoparticles are released. In this work, paint formulations containing the same amount of silicon dioxide (SiO2) nanoparticles but differing in the pigment volume concentration (PVC) and in amount and type of binder and pigment, were studied through leaching test to investigate the influence of these parameters on release of Si from paint. The results indicate greater release of Si, about 1.7wt.% of the SiO2 nanoparticles in the paint, for paint formulated with higher PVC value (63%), suggesting that the PVC is a crucial factor for release of SiO2 nanoparticles from paints. This hypothesis was also based on the fact that agglomerates of SiO2 nanoparticles were only found in leachates from paint with higher PVC. A paint sample with the higher amount of binder and less calcite filler exhibited a lower release of Si among the paints with a low PVC value (35%), and no SiO2 particles were detected in leachates collected from this paint. This could be due to the fact that a high portion of binder forms a suitable matrix to hold the SiO2 ENPs in paint. The paint sample in which the amount of calcite was partially substituted with TiO2 pigment did not show an important reduction on Si release. Our work suggests that paint debris containing SiO2 nanoparticles may release a limited amount of Si into the environment, and that by adjusting the properties of the binder in combination with common pigments it is possible to reduce the release of SiO2 nanoparticles. © 2014 Elsevier B.V.


Zuin S.,Venice Research Consortium | Micheletti C.,Venice Research Consortium | Critto A.,University of Venice | Pojana G.,University of Venice | And 4 more authors.
Nanotoxicology | Year: 2011

In assessing hazard for human health posed by newly engineered nanomaterials (ENM), approaches such as Weight of Evidence (WOE) and expert judgment are required to develop conclusions about the hazard of ENM. This is because all factors affecting hazard are not currently well defined and are often subject to different interpretation. Here we report the application of a WOE procedure to assess the potential of ENM to cause harm for human health, by integrating and combining physicochemical properties of NM and toxicity data obtained within the EU-funded Particle Risk project. The procedure was applied to carbon black (CB), single-walled carbon nanotubes (SWNT), C60 fullerene and quantum dots (QD) ENM tested during the Particle Risk project. The results show that some of the investigated ENM present a relatively higher hazardousness level on the basis of the integration of their physicochemical properties and toxicological effects, and that their hazard may be ranked as follow: QD ≫ C60 > SWNT > CB. This case study shows the utility of WOE approach to obtain a hazard ranking of ENM. © 2011 Informa UK, Ltd.


Kaiser J.-P.,Empa - Swiss Federal Laboratories for Materials Science and Technology | Zuin S.,Venice Research Consortium | Wick P.,Empa - Swiss Federal Laboratories for Materials Science and Technology
Science of the Total Environment | Year: 2013

Many paints for indoor and outdoor applications contain biocides and additives for protection against microbial, physical and chemical deterioration. The biocides should remain active as long as they are incorporated in the paint. Protection against microbial colonization should last at least a decade. Once the biocides are released they should degrade within a short time so that no accumulation in the environment can occur.The paint industry is not only focusing their research in producing better paint formulations with degradable biocides: they also consider using nanomaterials, such as nanosilver, nanocopper, nanozinc oxide, photocatalytic-active nanotitanium dioxide and nanosilica dioxide as additives for the protection of paints, against microbial degradation and physical and chemical deterioration. In the future nanomaterials should replace biodegradable biocides and improve the paint properties as well as impede colonization by microorganisms.At the time there is no guarantee that the nanomaterials in paints and façades will fulfill their task in the long run, since there are no long term studies available. From nanosilver doped paints it is known that silver is easily washed out by rain. Photocatalytic active nanotitanium dioxide adsorbs ultra violet light (UV-light) and generates hydroxyl radicals, which not only inhibit microbial growth but can also initiate or accelerate the photocatalytic degradation of the paint matrix. Thus at this time it is still unknown if it makes sense to incorporate nanomaterials into paints. Intensive research and development are still needed in order to find the answers. © 2012 Elsevier B.V.


Faggian V.,Venice Research Consortium | Scanferla P.,Venice Research Consortium | Paulussen S.,VITO NV | Zuin S.,Venice Research Consortium
Journal of Cleaner Production | Year: 2014

Membranes are permeable or semi-permeable barriers used to separate a wide range of particulate and dissolved compounds in liquid or gas. Polymeric membranes for water applications are arousing great interest as potentially cost-effective answers to a growing range of separation needs in different sectors. Although the polymeric membrane is not considered as toxic, the raw materials and additives used during the membrane manufacturing could be hazardous for human health and the environment. The aim of the present study was to evaluate the toxicity and ecotoxicity of chemicals used for phase inversion manufacturing of polyvinylidene difluoride (PVDF) and polyethersulfone (PES) membrane, and the REACH compliance analysis of these chemicals and membrane. The results show that 2 of 9 substances, the N,N-Dimethylacetamide (DMA) and 1-Methyl-2-pyrrolidone (NMP) solvents used for, or potentially present in, membrane are identified under REACH either as a substance of very high concern (SVHC). However, the identification of DMA and NMP as SVHC does not encompass any use restrictions. Among raw materials, the tetrahydrofuran (THF) showed evidence of carcinogenic potential, while the toluene of possible reproductive toxicant. Washing and drying procedures are usually applied by manufacturer to remove solvents to the extent possible. However, how residual solvents may be released during the life cycle of membrane and affect membrane toxicology profile are still open issues. In summary, we argue that to improve sustainable of phase inversion membrane, it is necessary to minimize the input of hazardous solvents, and to simultaneously stimulate the search for alternative eco-friendly solvents. © 2014 Elsevier Ltd. All rights reserved.


Al-Kattan A.,Empa - Swiss Federal Laboratories for Materials Science and Technology | Wichser A.,Empa - Swiss Federal Laboratories for Materials Science and Technology | Vonbank R.,Empa - Swiss Federal Laboratories for Materials Science and Technology | Brunner S.,Empa - Swiss Federal Laboratories for Materials Science and Technology | And 3 more authors.
Environmental Sciences: Processes and Impacts | Year: 2013

The release of nanomaterials from products and applications that are used by industry and consumers has only been studied to a very limited extent. The amount and the characteristics of the released particles determine the potential environmental exposure. In this work we investigated the release of Ti from paints containing pigment-TiO2 and nano-TiO2. Panels covered with paint with and without nano-TiO2 were exposed to simulated weathering by sunlight and rain in climate chambers. The same paints were also studied in small-scale leaching tests to elucidate the influence of various parameters on the release such as composition of water, type of support and UV-light. Under all conditions we only observed a very low release close to background values, less than 1.5 μg l-1 in the climate chamber over 113 irrigations per drying cycle and between 0.5 and 14 μg l -1 in the leaching tests, with the highest concentrations observed after prolonged UV-exposure. The actual release of Ti over the 113 weathering cycles was only 0.007% of the total Ti, indicating that TiO2 was strongly bound in the paint. Extraction of UV-exposed and then milled paint resulted in about 100-times larger release of Ti from the nano-TiO2 containing paint whereas the paint with only pigment-TiO2 did not show this increase. This indicated that the release of Ti from the paints is an effect of the addition of nano-TiO2, either by photocatalytic degradation of the organic paint matrix (observed by electron microscopic imaging of the paint surface) or by direct release of nano-TiO2. Our work suggests that paints containing nano-TiO2 may release only very limited amounts of materials into the environment, at least over the time-scales investigated in this work. © 2013 The Royal Society of Chemistry.


Massari A.,Venice Research Consortium | Beggio M.,Venice Research Consortium | Hreglich S.,Glass Research Facility | Marin R.,University of Venice | Zuin S.,Venice Research Consortium
Waste Management | Year: 2014

In order to assess the potential impacts posed by products containing engineered nanoparticles, it is essential to generate more data about the release of these particles from products' life cycle. Although first studies were performed to investigate the release of nanoparticles from use phase, very few data are available on the potential release from recycling or disposal of nano-enhanced products. In this work, we investigated the behavior of TiO2 nanoparticles from incineration of solid paint waste containing these particles. Solid paint debris with and without TiO2 nanoparticles were treated in a lab scale incineration plant at 950°C (combustion temperature) and in oxidizing atmosphere. The obtained ashes were also vitrified with additives and the release of Ti was finally evaluated by leaching test. From our incineration lab-scale experiment, we did not observe a release of TiO2 nanoparticles into the atmosphere, and Ti was attached to the surface of obtained solid residues (i.e. ashes). The characterization of ashes showed that TiO2 nanoparticles reacted during the incineration to give calcium titanate. Finally, a very low release of Ti was measured, less 1mg/kg, during the leaching test of ashes vitrified with glass cullet and feldspathic inert. Our work suggests that TiO2 nanoparticles added in paints may undergo to physicochemical transformation during the incineration, and that Ti found in ashes may be strongly immobilized in glass matrix. Since this conclusion is based on lab-scale experiment, further research is required to identify which nanoparticles will be emitted to the environment from a real-word-incineration system of household hazardous waste. © 2014 Elsevier Ltd.

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