Andrea Ulrich

Synthetic TiO2 nanoparticle emission from exterior facades into the aquatic environment

We present direct evidence of the release of synthetic nanoparticles from urban applications into the aquatic environment. We investigated TiO(2) particles as these particles are used in large quantities in exterior paints as whitening pigments and are to some extent also present in the nano-size range. TiO(2) particles were traced from exterior facade paints to the discharge into surface waters. We used a centrifugation based sample preparation which recovers TiO(2) particles between roughly 20 and 300nm. Analytical electron microscopy revealed that TiO(2) particles are detached from new and aged facade paints by natural weather conditions and are then transported by facade runoff and are discharged into natural, receiving waters. Microscopic investigations are confirmed by bulk chemical analysis. By combining results from microscopic investigations with bulk chemical analysis we calculated the number densities of synthetic TiO(2) particles in the runoff.

Application of an asymmetric flow field flow fractionation multi-detector approach for metallic engineered nanoparticle characterization – Prospects and limitations demonstrated on Au nanoparticles

In this work we discuss about the method development, applicability and limitations of an asymmetric flow field flow fractionation (A4F) system in combination with a multi-detector setup consisting of UV/vis, light scattering, and inductively coupled plasma mass spectrometry (ICPMS). The overall aim was to obtain a size dependent-, element specific-, and quantitative method appropriate for the characterization of metallic engineered nanoparticle (ENP) dispersions. Thus, systematic investigations of crucial method parameters were performed by employing well characterized Au nanoparticles (Au-NPs) as a defined model system. For good separation performance, the A4F flow-, membrane-, and carrier conditions were optimized. To obtain reliable size information, the use of laser light scattering based detectors was evaluated, where an online dynamic light scattering (DLS) detector showed good results for the investigated Au-NP up to a size of 80 nm in hydrodynamic diameter. To adapt large sensitivity differences of the various detectors, as well as to guarantee long term stability and minimum contamination of the mass spectrometer a split-flow concept for coupling ICPMS was evaluated. To test for reliable quantification, the ICPMS signal response of ionic Au standards was compared to that of Au-NP. Using proper stabilization with surfactants, no difference for concentrations of 1-50 μg Au L(-1) in the size range from 5 to 80 nm for citrate stabilized dispersions was observed. However, studies using different A4F channel membranes showed unspecific particle-membrane interaction resulting in retention time shifts and unspecific loss of nanoparticles, depending on the Au-NP system as well as membrane batch and type. Thus, reliable quantification and discrimination of ionic and particular species was performed using ICPMS in combination with ultracentrifugation instead of direct quantification with the A4F multi-detector setup. Figures of merit were obtained, by comparing the results from the multi detector approach outlined above, with results from batch-DLS and transmission electron microscopy (TEM). Furthermore, validation performed with certified NIST Au-NP showed excellent agreement. The developed methods show potential for characterization of other commonly used and important metallic engineered nanoparticles.

Modeling the flows of engineered nanomaterials during waste handling

Little is known about the behavior of engineered nanomaterials (ENM) at the interface from the technosphere to the ecosphere. Previous modeling of ENM flows to the environment revealed that significant amounts of ENM enter the waste stream and therefore waste incineration plants and landfills. It is the aim of this study to model the flows of ENM during waste incineration and landfilling in greater depth by including a more detailed description of the different processes and considering ENM-specific transformation reactions. Four substances were modeled: nano-TiO2, nano-ZnO, nano-Ag and carbon nanotube (CNT). These ENM are representative for commonly used materials and products, illustrating a variety of ENM with different behavior. The modeling was performed for Switzerland where almost 100% of the municipal waste and sewage sludge are burned. The mass-based modeling showed that – despite several differences among the models for nano-TiO2, nano-ZnO and nano-Ag (e.g. partial dissolution of nano-ZnO in acid washing of exhaust air or fly ash) – the major ENM flows go from the waste incineration plant to the landfill as bottom ash. All other flows within the system boundary (e.g. with the fly ash) were predicted to be about one magnitude smaller than the bottom ash flow. A different ENM distribution was found for CNTs that are expected to burn to a large extent (94%) so that only insignificant amounts remain in the system. The results of the modeling show that waste incineration can have a strong influence on some ENM but that still the majority of the ENM-mass is expected to end up in landfills.

Behavior of TiO2 Released from Nano-TiO2-Containing Paint and Comparison to Pristine Nano-TiO2

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-TiO2 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, ζ 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.

Impact of Low- and High-Oxidation Diesel Particulate Filters on Genotoxic Exhaust Constituents

Diesel exhaust contains several genotoxic compounds that may or may not penetrate diesel particulate filters (DPFs). Furthermore, the DPF-supported combustion of soot and adsorbed compounds may lead to the formation of additional pollutants. Herein, we compare the impact of 14 different DPFs on emissions of known genotoxic compounds. During a four year period, these DPFs were tested on a heavy duty diesel engine, operated in the ISO 8178/4 C1 cycle. Integral samples, including gas-phase and particle-bound matter were taken. All DPFs were efficient wall-flow filters with solid particulate number filtration efficiencies eta > 98%. On the basis of their CO, NO, and NO(2) emission characteristics, two different filter families were distinguished. DPFs with high oxidation potential (hox, n = 8) converted CO and NO besides hydrocarbons, whereas low oxidation potential DPFs (lox, n = 6) did not support CO and NO oxidation but still converted hydrocarbons. Lox-DPFs reduced NO(2) from 1.0 +/- 0.3 (engine-out) to 0.42 +/- 0.11 g/kWh (eta = 0.59), whereas hox-DPFs induced a NO(2) formation up to 3.3 +/- 0.7 g/kWh (eta = -2.16). Emissions of genotoxic PAHs decreased for both filter families. Conversion efficiencies varied for individual PAHs and were lower for lox- (eta = 0.31-0.87) than for hox-DPFs (eta = 0.75-0.98). Certain nitro-PAHs were formed indicating that nitration is an important step along PAH oxidation. For example, 1-nitronaphthalene emissions increased from 11 to 17 to 21 microg/L without, with lox-, and hox-DPFs respectively, whereas 2-nitronaphthalene emissions decreased from 25 to 19 to 4.7 microg/L. In contrast to our expectations, the nitration potential of lox-DPFs was higher than the one of hox-DPFs, despite the intense NO(2) formation of the latter. The filters converted most genotoxic PAHs and nitro-PAHs and most soot particles, acting as carriers for these compounds. Hox-DPF exhaust remains oxidizing and therefore is expected to support atmospheric oxidation reactions, whereas lox-DPF exhaust is reducing and consuming oxidants such as ozone, when mixed with ambient air.

Characterization of materials released into water from paint containing nano-SiO2.

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.

Release and environmental impact of silver nanoparticles and conventional organic biocides from coated wooden façades

This study represents for the first time a comprehensive assessment of functionality and environmental impacts of metallic silver nanoparticles (Ag-NP) compared to conventional organic biocides. Four different transparent, hydrophobic coatings of wooden outdoor façades were tested during one year outdoor weathering. The total silver release from products with Ag-NP was proportional to the overall erosion of the coating. The results indicate that the Ag-NPs are likely transformed to silver complexes, which are considerably less toxic than ionic silver. The protective effect of the silver containing coatings against mold, blue stain and algae was insufficient, even in immaculate and non-weathered conditions. The release of organic biocides from conventional coatings was dependent on the weather conditions, the type of biocide and the use in the base or top coat. The conventional coating showed a good overall performance free from mold, blue stain and algae until the end of the test period.

Human exposure to conventional and nanoparticle-containing sprays - A critical review

The release of pesticides from conventional spray products has been investigated in depth, and suitable analytical techniques detecting the mass of the released substances are available. In contrast, nanoparticle-containing sprays are less studied, although they are perceived as critical for consumers because inhalation exposure can occur to potentially toxic nanoparticles. A few recent studies presented analytical concepts for exposure experiments and generated data for exposure assessment. This study attempts to review and compare the current approaches to characterize nanosprays and to identify challenges for future research. Furthermore, experimental setups used for exposure assessment from conventional sprays are reviewed and compared to setups used for nanoparticle-containing sprays. National and international norms dealing with nanoparticle characterization, spray characterization and exposure are inspected with regard to their usefulness for standardizing exposure assessment. Different approaches in the field of exposure modeling are reviewed and compared. The conclusion is that due to largely varying experimental setups to date exposure values for nanosprays are difficult to compare. All studies are only conducted with a limited set of sprays, and no systematic evaluation of the study conditions is available. A suitable set of experimental setups as well as minimum reporting requirements should be agreed upon to enable the systematic evaluation of consumer sprays in the future. Indispensable features of such experimental setups are developed in this review.

Membrane-particle interactions in an asymmetric flow field flow fractionation channel studied with titanium dioxide nanoparticles.

Asymmetric flow field flow fractionation operated in a multidetector approach (A4F-MDA) is a powerful tool to perform size-classified nanoparticle analysis. Recently several publications mentioned insufficient recovery rates and even retention time shifts attributed to unspecific membrane-particle interactions. One hypothesis to explain this phenomenon is based on the surface charge (zeta-potential) of the membrane material and the particle. In this study, we investigated in how far the ζ-potential of A4F membrane and particles would determine the outcome of A4F in terms of feasibility, separation efficiency, retention time, and recovery rate, or whether other factors such as membrane morphology and particle size were equally important. We systematically studied the influence of the ζ-potential on the interactions between the most commonly used A4F membrane materials and two representative types of titanium dioxide nanoparticles (TiO2 NP). Furthermore the effect of different carrier media and additional surfactants on the surface charge of membranes and particles was investigated and the influence of the particle size and the particle concentration on the recovery rate was evaluated. We found that the eligibility of an A4F method can be predicted based on the ζ-potential of the NPs and the A4F membrane. Furthermore knowing the ζ-potential allows to tuning the separation efficiency of an A4F method. On the other hand we observed significant shifts in retention time for different membrane materials that impede the determination of particle size based on the classical A4F theory. These shifts cannot be attributed to the ζ-potential. Also the ζ-potential does not account for varying recovery rates of different particle types, instead the particle size seems to be the limiting factor. Therefore, the proper characterization of a polydisperse sample remains a challenge.

Effects of a combined Diesel particle filter-DeNOx system (DPN) on reactive nitrogen compounds emissions: a parameter study.

The impact of a combined diesel particle filter-deNO(x) system (DPN) on emissions of reactive nitrogen compounds (RNCs) was studied varying the urea feed factor (α), temperature, and residence time, which are key parameters of the deNO(x) process. The DPN consisted of a platinum-coated cordierite filter and a vanadia-based deNO(x) catalyst supporting selective catalytic reduction (SCR) chemistry. Ammonia (NH₃) is produced in situ from thermolysis of urea and hydrolysis of isocyanic acid (HNCO). HNCO and NH₃ are both toxic and highly reactive intermediates. The deNO(x) system was only part-time active in the ISO8178/4 C1cycle. Urea injection was stopped and restarted twice. Mean NO and NO₂ conversion efficiencies were 80%, 95%, 97% and 43%, 87%, 99%, respectively, for α = 0.8, 1.0, and 1.2. HNCO emissions increased from 0.028 g/h engine-out to 0.18, 0.25, and 0.26 g/h at α = 0.8, 1.0, and 1.2, whereas NH₃ emissions increased from <0.045 to 0.12, 1.82, and 12.8 g/h with maxima at highest temperatures and shortest residence times. Most HNCO is released at intermediate residence times (0.2-0.3 s) and temperatures (300-400 °C). Total RNC efficiencies are highest at α = 1.0, when comparable amounts of reduced and oxidized compounds are released. The DPN represents the most advanced system studied so far under the VERT protocol achieving high conversion efficiencies for particles, NO, NO₂, CO, and hydrocarbons. However, we observed a trade-off between deNO(x) efficiency and secondary emissions. Therefore, it is important to adopt such DPN technology to specific application conditions to take advantage of reduced NO(x) and particle emissions while avoiding NH₃ and HNCO slip.