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Given the recent increase in the demand for gallium nitride (GaN) in different markets like optoelectronics and power devices, the request for epitaxially grown GaN will further increase. To meet this high demand, higher throughput and more economical manufacturing technologies must be advanced. In this work, GaN thin films are deposited by reactive sputter deposition from a liquid gallium target at a substrate temperature of 900 °C. The layers are grown epitaxially on c-plane oriented sapphire in an industrial-scale sputter tool from Evatec AG. Due to the growth rate of >1 nm/s and the fast substrate heat-up time, the throughput in a production setup can be increased compared to other GaN growth techniques. The resistivity of the intrinsic insulating GaN can be lowered by intentional Si doping during the sputter deposition process by three orders of magnitude. Thereby, conductive n-type GaN can be grown with different dopant amounts. The carrier mobility of the sputter deposited film is 45 cm2 V−1 s−1 at a carrier concentration of 1.1 × 1020 cm−3 based on room temperature Hall measurements using a van der Pauw geometry. The lowest resistivity reaches 1300 μΩ cm, which is confirmed by sheet resistance measurements. Undoped films exhibit an x-ray diffraction rocking curve full width at half maximum of 0.2°, which increases up to 0.5° for highly Si-doped layers. The presented results show that GaN prepared by reactive sputter deposition from a liquid gallium source is a viable alternative to conventional deposition techniques for GaN.

Hitherto, there are only few studies that have analysed the variation of P contents in individual tree rings to reconstruct fluctuations in soil P availability. Therefore, this pilot study aimed to assess the relationship between changes in P content in tree rings and known changes in soil P availability resulting from fertilization of Norway spruce (Picea abies) and Scots pine (Pinus sylvestris) in fertilization trials at two different sites. We compared P contents in single tree rings from fertilized and unfertilized plots formed before and after P fertilization and assessed (1) whether fertilization leads to an immediate increase in P uptake and higher P contents in tree rings formed after fertilization, and (2) whether P is translocated to older tree rings that were formed before fertilization. After application of 70 kg P ha−1, a prompt and extended increase in relative wood P contents could be observed in both Norway spruce and Scots pine. However, only at the Norway Spruce site, this increase could be properly assigned to a P fertilization signal in heartwood rings formed after fertilization. In sapwood rings, however, P fertilization signals were masked by the inherent increase in P content from older towards younger sapwood rings, which was at least one order of magnitude higher than the increase from fertilization. We could not observe a P translocation into older tree rings, which existed as sapwood rings at the time of fertilization. This pilot study underlines the potential of dendrochemistry for reconstructing changes in soil P availability and improves the conceptual basis for further dendrochemical research, not only in fertilized but also in unfertilized forest ecosystems.

High-Z metal oxide nanoparticles hold promise as imaging probes and radio-enhancers. Hafnium dioxide nanoparticles have recently entered clinical evaluation. Despite promising early clinical findings, the potential of HfO2 as a matrix for multimodal theranostics is yet to be developed. Here, we investigate the physicochemical properties and the potential of HfO2-based nanoparticles for multimodal theranostic imaging. Undoped and lanthanide (Eu3+, Tb3+, and Gd3+)-doped HfO2 nanoparticles were synthesized and functionalized with various moieties including poly(vinylpyrrolidone) (PVP), (3-aminopropyl)triethoxysilane (APTES), and folic acid (FA). We show that different synthesis routes, including direct precipitation, microwave-assisted synthesis, and sol-gel chemistry, allow preparation of hafnium dioxide particles with distinct physicochemical properties. Sol-gel based synthesis allows preparation of uniform nanoparticles with dopant incorporation efficiencies superior to the other two methods. Both luminescence and contrast properties can be tweaked by lanthanide doping. We show that MRI contrast can be unified with radio-enhancement by incorporating lanthanide dopants in the HfO2 matrix. Importantly, ion leaching from the HfO2 host matrix in lysosomal-like conditions was minimal. For Gd:HfO2 nanoparticles, leaching was reduced >10× compared to Gd2O3, and no relevant cytotoxic effects have been observed in monocyte-derived macrophages for nanoparticle concentrations up to 250 μg/mL. Chemical surface modification allows further tailoring of the cyto- and hemocompatibility and enables functionalization with molecular targeting entities, which lead to enhanced cellular uptake. Taken together, the present study illustrates the manifold properties of HfO2-based nanomaterials with prospective clinical utility beyond radio-enhancement.

Accidental or open waste burning and incineration of nano-enabled products (NEPs) might lead to the release of incidental nanomaterials (NMs) into the environment resulting in harmful effects on humans. We have investigated combustion-generated NM release during accidental burning for several real-life NEPs such as paints with silica (SiO2) and spruce wood panels containing SiO2 and Fe2O3 NMs, paper with SiO2 and Fe2O3 NMs and polymeric composites with CuPhthtalocyanine NMs in poly lactic acid (PLA), polyamide 6 (PA6) and thermoplastic pol-urethane (TPU) matrices.Chemical compositions, aerosols number emission factors (nefs) and concentrations of the signature elements of the NMs of the combustion-generated aerosols were investigated. In addition, the residual ash was analyzed. The outcomes of this study shed light on how NM and matrix types influenced the properties of the released aerosols. Based on our results it was established that the combustion-generated aerosols were composed of transformed NMs with modified physical-chemical characteristics compared to the pristine NMs. In addition to the transformed NMs, there were also particles due to incomplete combustion of the matrix. Types of the pristine NMs and matrices affected the characteristics of the released aerosols. Since the hazard of the aerosols is related to the inhaled aerosol number concentration, the nef is an important parameter. Our results showed that the nefs in the size range of 5.6 to 560 nm depended strongly on the type of combusted NEP, which indicated that the NEPs could be categorized according to their potential to release aerosols in this size range when they were burnt. The generated release data facilitate the assessment of human and environmental exposure and the associated risk assessment of combustion-generated aerosols from NEPs.

Direct nano-scale microanalysis is important for photovoltaic functional thin films to characterize their homogeneity and purity. This demands combining spatial resolution in the micro/nano-scale and sensitivity in the trace-level range, which is at the moment beyond state-of-the-art. As dictated by counting statistics, the reduction of the spot size degrades the detection limit. The utilization of a tabletop XUV laser at λ = 46.9 nm has shown to dramatically improve the ablation efficiency with respect to that of visible lasers, such that ablation spot of 1 μm limits. Li-doped Cu2ZnSn(S,Se)4 (so-called kesterite) thin films were irradiated across 3D ablation arrays for hyperspectral mapping by means of time-of-flight mass spectrometry. The nominal 3D data node lattices were the initialisation perceptron, filled with measured values, and for a detailed supervised learning postprocessing, the node-to-node links were analysed by means of a 2D-kernel covariance algorithm. The latter permitted to obtain robust 3D elemental distribution functions well below the measurement spacing, giving insights into the inhomogeneity and impurities.

With the extensive use of silver nanoparticles (AgNPs) in various consumer products their potential toxicity is of great concern especially for highly sensitive population groups such as pregnant women and even the developing fetus. To understand if AgNPs are taken up and cross the human placenta, we studied their translocation and accumulation in the human ex vivo placenta perfusion model by single particle ICP-MS (spICP-MS). The impact of different surface modifications on placental transfer was assessed by AgNPs with two different modifications: polyethylene glycol (AgPEG NPs) and sodium carboxylate (AgCOONa NPs). AgNPs and ionic Ag were detected in the fetal circulation in low but not negligible amounts. Slightly higher Ag translocation across the placental barrier for perfusion with AgPEG NPs and higher AgNP accumulation in placental tissue for perfusion with AgCOONa NPs were observed. Since these AgNPs are soluble in water, we tried to distinguish between the translocation of dissolved and particulate Ag. Perfusion with AgNO3 revealed the formation of Ag containing NPs in both circulations over time, of which the amount and their size in the fetal circulation were comparable to those from perfusion experiments with both AgNP types. Although we were not able to clarify whether intact AgNPs and/or Ag precipitates from dissolved Ag cross the placental barrier, our study highlights that uptake of Ag ions and/or dissolution of AgNPs in the tissue followed by re-precipitation in the fetal circulation needs to be considered as an important pathway in studies of AgNP translocation across biological barriers.

Laser-induced breakdown spectroscopy (LIBS) is a well-established elemental analysis method, thanks to negligible sample preparation, rapid analysis, and a spatially resolved sensitivity down to trace level, in any kind of matrix. State-of-the-art LIBS is operated in the optical spectral range (UV-VIS). Unfortunately, the measurement precision is limited by the moderate stability and repeatability of the plasma emission. The detection and sensitivity to crucial elements such as light elements and halogens are also limited. This is particularly critical for inhomogeneous materials where signal fluctuation is related to the spatial elemental distribution. To overcome these disadvantages specific, LIBS techniques arrangement are often required. Laser-induced XUV Spectroscopy (LIXS) has some intrinsic advantages for overcoming some of the above mentioned limitations and it can support the spectroscopic information collected in the UV-VIS range.

Titanium dioxide nanoparticles (TiO2 NPs) are widely incorporated in various consumer products such as cosmetics and food. Despite known human exposure, the potential risks of TiO2 NPs during pregnancy are not fully understood, but several studies in mice elucidated toxic effects on fetal development. It has also been shown that modifying NPs with positive or negative surface charge alters cellular uptake and abolishes fetotoxicity of silicon dioxide (SiO2) NPs in mice. Here, we investigated accumulation and translocation of positively charged TiO2-NH2 and negatively charged TiO2-COOH NPs at the placental barrier, to clarify whether surface charge provides a means to control TiO2 NP distribution at the placental barrier. To ensure outcome relevant for humans, the recently developed in vitro human placental co-culture model and the gold standard amongst placental translocation models – the ex vivo perfusion of human term placental tissue – were employed during this study. Sector field-ICP-MS analysis of maternal and fetal supernatants as well as placental cells/tissues revealed a substantial accumulation of both TiO2 NP types while no considerable placental translocation was apparent in both models. Characterization of agglomeration behavior demonstrated a strong and fast agglomeration of TiO2-NH2 and TiO2-COOH NPs in the different culture media. Overall, our results indicate that surface charge is not a key factor to steer placental uptake and transfer of TiO2. Moreover, the negligible placental transfer but high accumulation of TiO2 NPs in placental tissue suggests that potential effects on fetal health may occur indirectly, which calls for further studies elucidating the impact of TiO2 NPs on placental tissue functionality and signaling.

There is increasing evidence that certain nanoparticles (NPs) can overcome the placental barrier, raising concerns on potential adverse effects on the growing fetus. But even in the absence of placental transfer, NPs may pose a risk to proper fetal development if they interfere with the viability and functionality of the placental tissue. The effects of NPs on the human placenta are not well studied or understood, and predictive in vitro placenta models to achieve mechanistic insights on NP-placenta interactions are essentially lacking. Using the scaffold-free hanging drop technology, we developed a well-organized and highly reproducible 3D co-culture microtissue (MT) model consisting of a core of placental fibroblasts surrounded by a trophoblast cell layer, which resembles the structure of the in vivo placental tissue. We could show that secretion levels of human chorionic gonadotropin (hCG) were significantly higher in 3D than in 2D cell cultures, which indicates an enhanced differentiation of trophoblasts grown on 3D MTs. NP toxicity assessment revealed that cadmium telluride (CdTe) and copper oxide (CuO) NPs but not titanium dioxide (TiO2) NPs decreased MT viability and reduced the release of hCG. NP acute toxicity was significantly reduced in 3D co-culture MTs compared to 2D monocultures. Taken together, 3D placental MTs provide a new and promising model for the fast generation of tissue-relevant acute NP toxicity data, which are indispensable for the safe development of NPs for industrial, commercial and medical applications.

The water column of Lake Baikal (Siberia) is pervasively oxic and O2 penetrates several cm into the sediment, followed by distinct layers of Fe/Mn oxide that undergo reductive-dissolution/oxidative-precipitation cycles. Uranium (U) contents of the oxic surface sediment layers were ~ 15 μg g− 1, which is unparalleled in oxygenated lakes. To understand the processes leading to this enrichment we investigated the geochemical composition of the particulate matter and pore water of four sediment cores from different locations in the lake and performed mass balance calculations based on sediment mass accumulation rates and published loads from major tributaries. The comparison of loads and export of U in Lake Baikal suggested that current estimates of loads are too low by a factor of about 3 compared to sediment mass accumulation rates. Peak loads during spring ice melt in tributaries that are difficult to monitor and quantify might be the main cause for the deviation. The high U concentrations in the lake sediments originated from the scavenging of U in the water column through association with settling organic particles and particulate Fe(III)- and, to a lesser extent, Mn(IV)-oxides. We outline the hypothesis that two distinct U phases, lithogenic and non-lithogenic U reach the lake sediment and that authigenic U is subsequently formed under reducing conditions within the sediment. In some cores we found that most U was remobilized during the degradation of organic matter, in particular within the top oxygenated layer of the sediment. Significant enrichments prevailed due to U adsorption to and/or co-precipitation with Fe-oxides. When Fe-oxides and, to a lesser extent, Mn-oxides were reductively dissolved, they released U to the pore water, leading to peak dissolved U concentrations in the anoxic sediment, which in turn, precipitated as authigenic U under predominantly sulphate-reducing conditions. The onset of the accumulation of authigenic U coincided with the formation of distinct Fe/Mn oxide layers above. We argue that the resilience of Fe-oxides (especially crystalline goethite and hematite), in association with phosphate, even within reducing (but non-sulfidic) sediments support the burial of substantial amounts of U.

Fuel additives used in particle traps have to comply with environmental directives and should not support the formation of additional toxic substances. The emission of metal additives from diesel engines with downstream particle traps has been studied. Aspects of the optimisation of sampling procedure, sample preparation and analysis are described. Exemplary results in form of a mass balance calculation are presented. The results demonstrate the high retention rate of the studied filter system but also possible deposition of additive metals in the engine.

Due to their interesting physicochemical properties, gold nanoparticles (Au-NPs) are the focus of increasing attention in the field of biomedicine and are under consideration for use in drug delivery and bioimaging, or as radiosensitizers and nano-based vaccines. Thorough evaluation of the genotoxic potential of Au-NPs is required, since damage to the genome can remain undetected in standard hazard assessments. Available genotoxicity data is either limited or contradictory. Here, we examined the influence of three surface modified 3–4 nm Au-NPs on human A549 cells, according to the reactive oxygen species (ROS) paradigm. After 24 h of Au-NP treatment, nanoparticles were taken up by cells as agglomerates; however, no influence on cell viability or inflammation was detected. No increase in ROS production was observed by H2- DCF assay; however, intracellular glutathione levels reduced over time, indicating oxidative stress. All three types of Au- NPs induced DNA damage, as detected by alkaline comet assay. The strongest genotoxic effect was observed for positively charged Au-NP I. Further analysis of Au-NP I by neutral comet assay, fluorimetric detection of alkaline DNA unwinding assay, and γH2AX staining, revealed that the induced DNA lesions were predominantly at alkali-labile sites. As highly controlled repair mechanisms have evolved to remove a wide range of DNA lesions with great efficiency, it is important to focus on both acute cyto- and genotoxicity, alongside post-treatment effects and DNA repair. We demonstrate that Au-NPinduced DNA damage is largely repaired over time, indicating that the observed damage is of transient nature. published

Nanoparticles from a HD-Diesel engine and their composition were investigated in the present paper. Three variants of fuel additivities were applied to allow the balances of certain tracer-substances after the tests: 2% of additives-free lube oil; 2% of market lube oil with additive package and Fe-based regeneration additive (FBC) with 40 ppm Fe. The analysed SMPS particle size distributions indicated that by blending of the market lube oil to the fuel the combined effects of metals or metal oxides from the additive packages and of the heavy HC’s from the lube oil matrix contribute the most to the increase of nuclei mode. From the masses of Fe, Zn and Ca, which were introduced with the fuel, only parts were found as integral masses at all ELPI-stages – Fe 43.5%, Zn 36.6%, Ca 65.5%. The majority of mass of some metals, or metal oxides emissions on ELPI-stages (up to 80%) is in the size ranges below 100 nm.

The mechanism of the capacity degradation of LaNi5-based alloy electrodes was investigated with a special focus on the influence of the alloy and surface composition, as well as the unique structure obtained by gas atomisation. The electrochemical properties, especially the cycle life curve (i.e. the capacity as a function of the cycle number of LaNi4.5Al0.5, LaNi2.5Co2.4Al0.1, (La + Mm)Ni3.5Co0.7Al0.35Mn0.4Zr0.05, and MmNi4.3Al0.2Mn0.5 alloy electrodes), was analysed and modelled. The capacity degradation upon cycling is determined by the chemical state of the alloy elements and the solubility of their oxides. The cycle life curves for the alloy electrodes without Co exhibited a rapid activation (3–4 cycles to reach maximum capacity), as well as rapid degradation (130–180 cycles for 50% maximum discharge capacity). LaNi2.5Co2.4Al0.1 and (La + Mm)Ni3.5Co0.7Al0.35Mn0.4Zr0.05 alloy electrodes activated after 7–10 cycles and showed very stable discharge behaviour (more than 400 cycles). The Co-containing alloy electrodes primarily lose the cycle stability because of mechanical decrepitation, whereas the alloys without Co suffer from selective dissolution of the unstable elements in the potential window, which was shown by our model of alloy degradation and confirmed by means of SEM, WDX, and ICP-OES data.

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.

Weathering processes can influence the surface properties of composites with incorporated nanoparticles. These changes may affect the release behavior of nanoparticles when an abrasion process is applied. Therefore, the influence of two different weathering processes, immersion in water and exposure to UV light, on the properties of abraded particles from a carbon nanotube (CNT)/epoxy nanocomposite was investigated. The investigation included the measurement of the weathering impact on the surface chemistry of the exposed samples, the particle size of abraded particles, the quantity of exposed CNTs in the respirable part of the abraded particles, and the toxicity of abraded particles, measured by in vitro toxicity tests using the THP-1 monocyte-derived macrophages. The results showed that weathering by immersion in water had no influence on the properties of abraded particles. The exposure to UV light caused a degradation of the epoxy on the surface, followed by delamination of an approx. 2.5 μm thick layer. An increased quantity of exposed CNTs in abraded particles was not found; on the contrary, longer UV exposure times decreased the released fraction of CNTs from 0.6% to 0.4%. The toxicity tests revealed that abraded particles from the nanocomposites did not induce additional acute cytotoxic effects compared to particles from the neat epoxy.

Aim: Nanoparticle-based drug carriers hold great promise for the development of targeted therapies in pregnancy with reduced off-target effects. Here, we performed a mechanistic in vitro study on placental localization and penetration of gold nanoparticles (AuNPs) in dependence of particle size and surface modification. Materials & methods: AuNP uptake and penetration in human placental coculture microtissues was assessed by inductively coupled plasma-mass spectrometry, transmission electron microscopy and laser ablation-inductively coupled plasma-mass spectrometry. Results: Higher uptake and deeper penetration was observed for smaller (3–4 nm) or sodium carboxylate-modified AuNPs than for larger (13–14 nm) or PEGylate AuNPs, which barely passed the trophoblast barrier layer. Conclusion: It is possible to steer placental uptake and penetration of AuNPs by tailoring their properties, which is a prerequisite for the development of targeted therapies in pregnancy.

We report on theoretical and experimental considerations on bacteria capturing and enrichment via magnetic separation enabling integrated diagnosis and treatment of blood stream infections. We show optimization of carrier-pathogen interactions based on a mathematical model followed by an experimental proof-of-concept study along with investigations on the process safety.

This work describes an evaluation of a strategy for multi-elemental analysis of typical ancient bronzes (copper, lead bronze and tin bronze) by means of laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS).The samples originating from archeological experiments on ancient metal smelting processes using direct reduction in a ‘bloomery’ furnace as well as historical casting techniques were investigated with the use of the previously proposed analytical procedure, including metallurgical observation and preliminary visual estimation of the homogeneity of the samples. The results of LA-ICPMS analysis were compared to the results of bulk composition obtained by X-ray fluorescence spectrometry (XRF) and by inductively coupled plasma mass spectrometry (ICPMS) after acid digestion. These results were coherent for most of the elements confirming the usefulness of the proposed analytical procedure, however the reliability of the quantitative information about the content of the most heterogeneously distributed elements was also discussed in more detail.

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.

Lake Baikal is the deepest and probably oldest lake on Earth. Its water column is pervasively oxic and sedimentation rates are very low which leads to the formation of a dynamic iron (Fe) and manganese (Mn) enrichment below the Mn(II)/O2 boundary. These often massive accumulations can be buried within the reducing part of the sediments and give rise to complex and cryptic redox cycles. The mobility of rare earth elements (REEs) is influenced by the dissolution and reduction dynamics of the ferromanganese oxides. The present study offers an overview of the REE chemistry in Lake Baikal and its catchment area and more specifically REE distribution in five 11- to 26-cm-long sediment cores situated across the lake at different water depths. We analysed and discussed normalised REE patterns and their consequential cerium (Ce) anomalies. While particulate REE concentrations are mainly influenced by processes above or near the surface of Lake Baikal, such as the development of a widespread negative Ce anomaly, processes occurring during early diagenesis in the sediment are most reflected in pore water REEs. The dissolution of ferromanganese oxides at the Mn(II)/O2 boundary remobilizes significant amounts of REE into the pore water whereby some are likely adsorbed onto colloidal Fe oxides. However, besides the tendency of Ce being associated with Mn-oxides, pore water REEs fractionate predominantly around the buried Fe/Mn accumulation where light REEs preferentially adsorb onto Fe-oxides.

International audience; C3AH6 is a stable phase in the CaO-Al2O3-H2O system at temperatures 20 °C and above. The presence of SiO2 results in the formation of C3AH6 and C-S-H phases at room temperature. At 110 °C crystalline C3ASyH2(3 − y) phases form. Two solid solutions: C3AH6-C3AS0.41H5.18 and C3AS0.84H4.32-C3AS3 are found with log Ks0 = − 20.50, − 25.35, − 26.70 and − 39.7 at 20 °C, respectively. In the CaO-Fe2O3-H2O system, only traces of C3FH6 and C4FH13 phases are formed due to the high stability of FH phase. The presence of silica leads between 20 and 110 °C to the formation of C3FS0.84H4.32 and C3FS1.34H3.32 phases with log Ks0 = − 32.50 and − 34.20 at 25 °C. No significant solid solution formation occurred between C3AH6 and C3FH6 end members, but between C3AS0.84H4.32 and C3FS0.84H4.32 solid solution formation is observed. The determined solubility products indicate that C3FS0.84H4.32 is the most stable iron-containing phase in hydrated Portland cements.

The study explores the potential of cellulose nanocrystals (CNC), cellulose nanofibers (CNF) and chitin nanocrystals (ChNC) isolated from bioresidues to remove silver ions from contaminated water. Zeta sizer studies showed negatively charged surfaces for CNC and CNF isolated from cellulose sludge in the acidic and alkaline pHs, whereas ChNC isolated from crab shell residue showed either positive or negative charges depending on pH conditions. Model water containing silver ions showed a decrease in Ag+ ion concentration (measured by inductively coupled plasma-optical emission spectrometer; inductively coupled plasma mass spectrometry), after treatment with CNC, CNF and ChNC suspensions. The highest Ag+ ion removal was measured near neutral pH for CNC, being 34.4 mg/g, corresponding to 64 % removal. ChNC showed 37 % and CNF showed 27 % removal of silver ions. The WDX (wavelength dispersive X-ray analysis) and XPS (X-ray photoelectron spectroscopy) analysis confirmed the presence of silver ions on the surface of the nanocellulose and nanochitin after adsorption. Surface adsorption on the nanoparticles via electrostatic interactions is considered to be the prominent mechanism of heavy metal ion capture from aqueous medium, with CNC with negative surface charge and negatively charged functional groups being most favourable for the adsorption of positively charged Ag+ ions compared to other native bionanomaterials.

Background Nanosilver shows great promise for use in industrial, consumer or medical products because of its antimicrobial properties. However, the underlying mechanisms of the effects of silver nanoparticles on human cells are still controversial. Therefore, in the present study the influence of the chloride concentration and different serum content of culture media on the cytotoxic effects of nanosilver was systematically evaluated. Results Our results show that nanosilver toxicity was strongly affected by the composition of the culture media. The chloride concentration, as well as the carbon content affected the silver agglomeration and the complex formation. But also the dissolution of nanosilver and the availability of free silver ions (Ag+) were severely affected by the compositions of the culture media. Cells, only exposed to silver particles in suspension and dissolved silver complexes, did not show any effects under all conditions. Nanosilver agglomerates and silver complexes were not very soluble. Thus, cells growing on the bottom of the culture dishes were exposed to sedimented nanosilver agglomerates and precipitated silver complexes. Locally, the concentration of silver on the cell surface was very high, much higher compared the silver concentration in the bulk solution. The cytotoxic effects of nanosilver are therefore a combination of precipitated silver complexes and organic silver compounds rather than free silver ions. Conclusions Silver coatings are used in health care products due to their bacteriostatic or antibacterial properties. The assessment of the toxicity of a certain compound is mostly done using in vitro assays. Therefore, cytotoxicity studies of nanosilver using human cell cultures have to be undertaken under well controlled and understood cultivations conditions in order to improve the compatibility of different studies. Especially when eukaryotic versus prokaryotic systems are compared for the evaluation of the use of nanosilver as antibacterial coatings for implants in order to prevent bacterial colonization. Electronic supplementary material The online version of this article (doi:10.1186/s12951-016-0244-3) contains supplementary material, which is available to authorized users.

Background We investigated the particles released due to abrasion of wood surfaces pressure-treated with micronized copper azole (MCA) wood preservative and we gathered preliminary data on its in vitro cytotoxicity for lung cells. The data were compared with particles released after abrasion of untreated, water (0% MCA)-pressure-treated, chromated copper (CC)-pressure-treated wood, and varnished wood. Size, morphology, and composition of the released particles were analyzed. Results Our results indicate that the abrasion of MCA-pressure-treated wood does not cause an additional release of nanoparticles from the unreacted copper (Cu) carbonate nanoparticles from of the MCA formulation. However, a small amount of released Cu was detected in the nanosized fraction of wood dust, which could penetrate the deep lungs. The acute cytotoxicity studies were performed on a human lung epithelial cell line and human macrophages derived from a monocytic cell line. These cell types are likely to encounter the released wood particles after inhalation. Conclusions Our findings indicate that under the experimental conditions chosen, MCA does not pose a specific additional nano-risk, i.e. there is no additional release of nanoparticles and no specific nano-toxicity for lung epithelial cells and macrophages., Journal of Nanobiotechnology, 14 (1), ISSN:1477-3155

International audience; Monosulfate (3CaO*(AlxFe1x)2O3*CaSO4*12H2O) is an AFm phase that can be formed during the hydration of cement. Fe-containing monosulfate and (Al,Fe) mixed monosulfate were synthesized and characterized. Fe-monosulfate is composed of a positively charged main layer [Ca2Fe(OH)6]+ and a negatively charged interlayer [1/2SO4*3H2O]−, crystallizes in the trigonal R 3 symmetry, and is isotypic with Al-monosulfate. The solubility product at 25°C was determined to be 31.57. The formation of solid solution due to Al-Fe substitution in the main layer structure of monosulfate was observed. Based on the evolution of the unit cell parameters and the thermodynamic investigations, a presence of solid solution from 0.0 to 0.45 Al/(Al + Fe) ratio and a miscibility gap in the range 0.45 < Al/(Al + Fe) ratio

In this study, the chemical composition of PM10 at various sites in Switzerland during a one year period in 2008/2009 and changes since the time of a similar characterisation campaign in 1998/1999 are investigated. The concentrations of main components of PM10 were found to be similar at different site types north of the Alps (i.e. urban background, suburban and rural sites). Secondary inorganic PM10 components (nitrate, sulphate and ammonium) constituted the largest PM10 mass fraction, followed by carbonaceous matter (OM and EC), while the abundance of mineral dust and trace elements was small (both

The volcanic aerosol plume resulting from the Eyjafjallajökull eruption in Iceland in April and May 2010 was detected in clear layers above Switzerland during two periods (17–19 April 2010 and 16–19 May 2010). In-situ measurements of the airborne volcanic plume were performed both within ground-based monitoring networks and with a research aircraft up to an altitude of 6000 m a.s.l. The wide range of aerosol and gas phase parameters studied at the high altitude research station Jungfraujoch (3580 m a.s.l.) allowed for an in-depth characterization of the detected volcanic aerosol. Both the data from the Jungfraujoch and the aircraft vertical profiles showed a consistent volcanic ash mode in the aerosol volume size distribution with a mean optical diameter around 3 ± 0.3 μm. These particles were found to have an average chemical composition very similar to the trachyandesite-like composition of rock samples collected near the volcano. Furthermore, chemical processing of volcanic sulfur dioxide into sulfate clearly contributed to the accumulation mode of the aerosol at the Jungfraujoch. The combination of these in-situ data and plume dispersion modeling results showed that a significant portion of the first volcanic aerosol plume reaching Switzerland on 17 April 2010 did not reach the Jungfraujoch directly, but was first dispersed and diluted in the planetary boundary layer. The maximum PM10 mass concentrations at the Jungfraujoch reached 30 μgm−3 and 70 μgm−3 (for 10-min mean values) duri ng the April and May episode, respectively. Even low-altitude monitoring stations registered up to 45 μgm−3 of volcanic ash related PM10 (Basel, Northwestern Switzerland, 18/19 April 2010). The flights with the research aircraft on 17 April 2010 showed one order of magnitude higher number concentrations over the northern Swiss plateau compared to the Jungfraujoch, and a mass concentration of 320 (200–520) μgm−3 on 18 May 2010 over the northwestern Swiss plateau. The presented data significantly contributed to the time-critical assessment of the local ash layer properties during the initial eruption phase. Furthermore, dispersion models benefited from the detailed information on the volcanic aerosol size distribution and its chemical composition.

Long-term exposure to increased levels of reactive nitrogen compounds (RNCs) and particulate matter (PM) affect human health. Many cities are currently not able to fulfill European air quality standards for these critical pollutants. Meanwhile, promising new abatement technologies such as diesel particle filters (DPFs) and selective catalytic reduction (SCR) catalysts are developed to reduce PM and RNC emissions. Herein, effects of a urea-based SCR system on RNC emissions are discussed and we quantified the highly reactive intermediates isocyanic acid (HNCO) and ammonia (NH 3 ), both potential secondary pollutants of the urea-based SCR chemistry. A diesel engine (3.0 L, 100 kW), operated in the ISO 8178/4 C1, cycle was used as test platform. A V 2 O 5 -based SCR catalyst was either applied as such or down-stream of a high oxidation potential-DPF (hox-DPF). With active SCR, nitric oxide (NO) and nitrogen dioxide (NO 2 ) conversion efficiencies of 0.86–0.94 and 0.86–0.99 were obtained. On the other hand, mean HNCO and NH 3 emissions increased to 240–280 and 1800–1900 mg h −1 . On a molar basis, HNCO accounted for 0.8–1.4% and NH 3 for 14–25% of the emitted RNCs. On roads, SCR systems will partly be inactive when exhaust temperatures drop below 220 °C. The system was active only during 75% of the test cycle, and urea dosing was stopped and restarted several times. Consequently, NO conversion stopped but interestingly, NO 2 was still converted. Such light-off and shutdown events are frequent in urban driving, compromising the overall deNO x efficiency. Another important effect of the SCR technology is illustrated by the NH 3 /NO 2 ratio, which was >1 with active SCR, indicating that exhaust is basic rather than acidic after the SCR catalyst. Under these conditions, isocyanic acid is stable. The widespread use of various converter technologies already affected RNC release. Diesel oxidation catalysts (DOCs) and hox-DPFs increased NO 2 emissions, three-way catalysts (TWCs) those of NH 3 . The investigated SCR technology substantially lowered NO and NO 2 emissions, while NH 3 levels were comparable to those of TWC vehicles (300–1500 mg h −1 ). If applied in the future, the combined DPF/SCR technology will change ambient RNC levels, PM compositions and atmospheric redox- and acid/base-chemistry in traffic-affected areas.

All conventional piston-driven combustion engines emit metal oxide particles. The main sources are the abrasion between piston-ring and cylinder, abrasion in the bearings, catalyst coating, lube-oil additives, and fuel additives for promoting the exhaust-gas after-treatment. Metal oxides, especially from transition metals, are very toxic when they are very fine. These particles have a high BET surface and penetrate the biological system. Hence, these particles must be scrutinized for quantity, size distribution and composition. This paper draws from published data and mainly the VERT certification tests, which prescribe a size specific metal analysis. The total mass of metal oxide is 0.1 – 1 mg/km, which appears negligible. But these particles are in the 10 – 20 nm size range. Hence, this small mass represents 1015 particles per kilometer. This is approximately the same number as soot particles emitted by diesel engines. Public health should focus on the metal oxide particles that are smaller and probalby more toxic than the soot particles. SI engines run at higher RPM and therefore emit more metal oxide particles than Diesel engines. Highly efficient filtration of such particles seems therefore necessary for all engine categories

Studies combining both the quantification of free nanoparticle release and the toxicological investigations of the released particles from actual nanoproducts in a real-life exposure scenario are urgently needed, yet very rare. Here, a new measurement method was established to quantify the amount of free-standing and protruding multiwalled carbon nanotubes (MWCNTs) in the respirable fraction of particles abraded from a MWCNT–epoxy nanocomposite. The quantification approach involves the prelabeling of MWCNTs with lead ions, nanocomposite production, abrasion and collection of the inhalable particle fraction, and quantification of free-standing and protruding MWCNTs by measuring the concentration of released lead ions. In vitro toxicity studies for genotoxicity, reactive oxygen species formation, and cell viability were performed using A549 human alveolar epithelial cells and THP-1 monocyte-derived macrophages. The quantification experiment revealed that in the respirable fraction of the abraded particles, approximately 4000 ppm of the MWCNTs were released as exposed MWCNTs (which could contact lung cells upon inhalation) and approximately 40 ppm as free-standing MWCNTs in the worst-case scenario. The release of exposed MWCNTs was lower for nanocomposites containing agglomerated MWCNTs. The toxicity tests revealed that the abraded particles did not induce any acute cytotoxic effects., Environmental Science & Technology, 49 (17), ISSN:0013-936X, ISSN:1520-5851

Iron-catalyzed diesel particle filters (DPFs) are widely used for particle abatement. Active catalyst particles, so-called fuel-borne catalysts (FBCs), are formed in situ, in the engine, when combusting precursors, which were premixed with the fuel. The obtained iron oxide particles catalyze soot oxidation in filters. Iron-catalyzed DPFs are considered as safe with respect to their potential to form polychlorinated dibenzodioxins/furans (PCDD/Fs). We reported that a bimetallic potassium/iron FBC supported an intense PCDD/F formation in a DPF. Here, we discuss the impact of fatty acid methyl ester (FAME) biofuel on PCDD/F emissions. The iron-catalyzed DPF indeed supported a PCDD/F formation with biofuel but remained inactive with petroleum-derived diesel fuel. PCDD/F emissions (I-TEQ) increased 23-fold when comparing biofuel and diesel data. Emissions of 2,3,7,8-TCDD, the most toxic congener [toxicity equivalence factor (TEF) = 1.0], increased 90-fold, and those of 2,3,7,8-TCDF (TEF = 0.1) increased 170-fold. Congener patterns also changed, indicating a preferential formation of tetra- and penta-chlorodibenzofurans. Thus, an inactive iron-catalyzed DPF becomes active, supporting a PCDD/F formation, when operated with biofuel containing impurities of potassium. Alkali metals are inherent constituents of biofuels. According to the current European Union (EU) legislation, levels of 5 μg/g are accepted. We conclude that risks for a secondary PCDD/F formation in iron-catalyzed DPFs increase when combusting potassium-containing biofuels.

Mineral-based membranes for high temperature alkaline electrolysis were developed by a phase inversion process with polysulfone as binder. The long-term stability of new mineral fillers: wollastonite, forsterite and barite was assessed by 8000 h-long leaching experiments (5.5 M KOH, 85 degrees C) combined with thermodynamic modelling. Barite has released only 6.22 10-4 M of Ba ions into the electrolyte and was selected as promising filler material, due to its excellent stability. Barite-based membranes, prepared by the phase inversion process, were further studied. The resistivity of these membranes in 5.5 M KOH was investigated as a function of membrane thickness and total porosity, hydrodynamic porosity as well as gas purities determined by conducting electrolysis at ambient conditions. It was found that a dense top layer resulting from the phase inversion process, shows resistivity values up to 451.0 +/- 22 Omega cm, which is two orders of magnitude higher than a porous bulk membrane microstructure (3.89 Omega cm). Developed membranes provided hydrogen purity of 99.83 at 200 mA cm(-2), which is comparable to previously used chrysotile membranes and higher than commercial state-of-the-art Zirfon 500utp membrane. These cost-effective polysulfone - barite membranes are promising candidates as asbestos replacement for commercial applications. (C) 2015 Elsevier B.V. All rights reserved.

Questions about how to regulate nanoenhanced products regularly arise as researchers determine possible nanoparticle transformation(s). Focusing concern on the incorporation and subsequent release of nano-Ag in fabrics often overshadows the fact that many "conventional silver" antimicrobials such as ionic silver, AgCl, metallic Ag, and other forms will also form different species of silver. In this study we used a laboratory washing machine to simulate the household laundering of a number of textiles prepared with known conventional Ag or nano-Ag treatments and a commercially available fabric incorporating yarns coated with bulk metallic Ag. Serial filtration allowed for quantification of total Ag released in various size fractions (0.45 μm,0.45 μm,0.1 μm, and10 kDa), while characterization of particles with TEM/EDX provided insight on Ag transformation mechanisms. Most conventional Ag additives yielded more total Ag and more nanoparticulate-sized Ag in the washing liquid than fabrics that used nano-Ag treatments. Incorporating nano-silver into the fiber (as opposed to surface treatments) yielded less total Ag during fabric washing. A variety of metallic Ag, AgCl, and Ag/S particles were observed in washing solution by TEM/EDX to various extents depending on the initial Ag speciation in the fabrics. Very similar particles were also observed when dissolved ionic Ag was added directly into the washing liquid. On the basis of the present study, we can state that all silver-treated textiles, regardless of whether the treatment is "conventional" or "nano", can be a source of silver nanoparticles in washing solution when laundering fabrics. Indeed, in this study we observed that textiles treated with "conventional" silver have equal or greater propensity to form nano-silver particles during washing conditions than those treated with "nano"-silver. This fact needs to be strongly considered when addressing the risks of nano-silver and emphasizes that regulatory assessment of nano-silver warrants a similar approach to conventional silver.

An inventory of the copper-based metal objects of the megalithic necropolis of Sion/Petit-Chasseur has been compiled. 52 objects (or groups of objects) attributed to the Late Neolithic (Néolithique final valaisan), the Bell Beaker period and the Early Bronze Age have been identified. The inventory is completed by new analyses of the chemical composition undertaken for a sub-group of in total 27 lead isotope analyses and 35 chemical analyses in addition to the two lead isotope analyses and eleven chemical analyses already published. The results highlight that several sources of supply were used between the third millennium and the first half of the second millennium BC. With regard to the Late Neolithic period in Valais, the available data do not allow to determine whether copper ore or metal was used for the manufacturing of the tubular beads discovered in monument M XII of Sion/Petit-Chasseur III. A copper awl with a terminus ante quem at the beginning of the Early Bronze Age presents a chemical composition found again in the Late Neolithic of the Swiss Plateau. Although different possible sources can be taken into account at the European scale (Germany, Austria, Spain, Serbia), the prehistoric mine of Saint-Véran (Hautes-Alpes, France) is the closest one. The analyses of two pieces of the Early Bronze Age BzA1 (2200-2000 BC) reveal a quite particular copper known as “Singen type composition”. Though the lead isotope ratio measurements do not permit to identify the origin of the metal, they nonetheless indicate that these two artefacts are part of a network of raw material procurement, similar to the northern Alpine area evidenced by the site of Singen (Germany). With the start of the Early Bronze Age BzA2 (2000-1550 BC), the change of copper sources is accompanied by a technical evolution, the introduction of bronze technology. From that period on, supply of Valaisian copper cannot be excluded for most of the objects. However, lead isotope variation of local mineralisation is little specific and overlays many other European mineralisation patterns being also possible sources for this metal. An extraneous source, in the coastal part of Southern Tuscany, has been identified for one object. Five further other objects are possibly stemming from a blending of ores from the southern coast of Tuscany and other unidentified sources. Concerning the BzA2 period, the graves 2 and 3 of Sion/Petit-Chasseur I raise the question of the manufacturing of personal equipment. The grave goods deposited together with the buried individuals show homogeneous compositions, hardly compatible with progressive and random development of a personal equipment, but would rather mirror that they have been constituted during a short period of time, within a project.

Catalytic diesel particle filters (DPFs) have evolved to a powerful environmental technology. Several metal-based, fuel soluble catalysts, so-called fuel-borne catalysts (FBCs), were developed to catalyze soot combustion and support filter regeneration. Mainly iron- and cerium-based FBCs have been commercialized for passenger cars and heavy-duty vehicle applications. We investigated a new iron/potassium-based FBC used in combination with an uncoated silicon carbide filter and report effects on emissions of polychlorinated dibenzodioxins/furans (PCDD/Fs). The PCDD/F formation potential was assessed under best and worst case conditions, as required for filter approval under the VERT protocol. TEQ-weighted PCDD/F emissions remained low when using the Fe/K catalyst (37/7.5 μg/g) with the filter and commercial, low-sulfur fuel. The addition of chlorine (10 μg/g) immediately led to an intense PCDD/F formation in the Fe/K-DPF. TEQ-based emissions increased 51-fold from engine-out levels of 95 to 4800 pg I-TEQ/L after the DPF. Emissions of 2,3,7,8-TCDD, the most toxic congener (TEF = 1.0), increased 320-fold, those of 2,3,7,8-TCDF (TEF = 0.1) even 540-fold. Remarkable pattern changes were noticed, indicating a preferential formation of tetrachlorinated dibenzofurans. It has been shown that potassium acts as a structural promoter inducing the formation of magnetite (Fe3O4) rather than hematite (Fe2O3). This may alter the catalytic properties of iron. But the chemical nature of this new catalyst is yet unknown, and we are far from an established mechanism for this new pathway to PCDD/Fs. In conclusion, the iron/potassium-catalyzed DPF has a high PCDD/F formation potential, similar to the ones of copper-catalyzed filters, the latter are prohibited by Swiss legislation.

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 from0.045 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.

One of the AFm phases in hydrated Portland cement is Ca-3(AlxFe2-x)O-6 center dot CaCO3 center dot nH(2)O. It is based on hexagonal and platey structural elements and the interlayer structure incorporates CO32-. The solid phases were experimentally synthesized and characterized by different techniques including X-ray techniques (XRD and EXAFS) and vibrational spectroscopy techniques (IR, Raman). Fe-monocarbonate (Fe-Mc) and Al-monocarbonate (Al-Mc) were found to be stable up to 50 degrees C, while Fe-hemicarbonate (Fe-Hc) was unstable with respect to Fe-Mc in the presence of calcite. Fe-Mc has a rhombohedral R (3) over barc symmetry which is different from the triclinic of the Al analogue. Both XRD and thermodynamic modelling of the liquid compositions indicated that Al-Mc and the Fe-Mc phases do not form solid solution. The solubility products were calculated experimentally at 20 degrees C and 50 degrees C. Under standards condition the solubility products and other thermodynamic parameters were estimated using temperature-solubility product extrapolation and found to be logK(so) (Fe-Mc) = -34.59 +/- 0.50, logK(so) (Fe-Hc) = -30.83 +/- 0.50 and logK(so)(Al-Mc) = -31.32 +/- 0.50. (C) 2010 Elsevier Ltd. All rights reserved.

Ten Early Bronze Age (BzA1, 2200-2000 BC) copper artefacts from the central Valais region from Switzerland were studied for their elemental composition and lead isotope ratios. In order to answer the archaeological question of a local copper supply, a database for copper minerals across the Valais (Switzerland) has been established. This database contains 69 data on lead isotope ratios as well as additional information on the minerals and geochemical associations for copper minerals from 38 locations in the Valais. Comparisons of the artefacts were also made with data pertaining to minerals from various deposits from Europe and Anatolia taken from the literature. The provenance of the materials is very diverse. Some of the data are compatible with the data from the copper mineral deposits of the Valais region. Moreover, three copper lunulae were identified as possibly Tuscan, which suggests contacts between Italy and the Valais region. This pattern also establishes a multiplicity of provenances for the metal and cultural influences in the Alpine environment of the Rhone Valley of Switzerland at the beginning of the Early Bronze Age. © 2011 Elsevier Ltd.

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 eta98%. 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.

Diesel particulate filters (DPFs) are a promising technology to detoxify diesel exhaust. However, the secondary combustion of diesel soot and associated compounds may also induce the formation of new pollutants. Diesel soot is rated as carcinogenic to humans and also acts as a carrier for a variety of genotoxic compounds such as certain polycyclic aromatic hydrocarbons (PAHs) or nitrated PAHs (nitro-PAHs). Furthermore, diesel exhaust contains considerable amounts of nitric oxide (NO), which can be converted to more powerful nitrating species like nitrogen dioxide (NO2), nitric acid (HNO3), and others. This mix of compounds may support nitration reactions in DPFs. Herein we report effects of two cordierite-based, monolithic, wall-flow DPFs on emissions of genotoxic PAHs and nitro-PAHs and compare these findings with those of a reporter gene bioassay sensitive to aryl hydrocarbons (AHs). Soot combustion was either catalyzed with an iron- or a copper/iron-based fuel additive (fuel-borne catalysts). A heavy duty diesel engine, operated according to the 8-stage ISO 8178/4 C1 cycle, was used as test platform. Emissions of all investigated 4- to 6-ring PAHs were reduced by about 40-90%, including those rated as carcinogenic. Emissions of 1- and 2-nitronaphthalene increased by about 20-100%. Among the 3-ring nitro-PAHs, emissions of 3-nitrophenanthrene decreased by about 30%, whereas 9-nitrophenanthrene and 9-nitroanthracene were found only after DPFs. In case of 4-ring nitro-PAHs, emissions of 3-nitrofluoranthene, 1-nitropyrene, and 4-nitropyrene decreased by about 40-60% with DPFs. Total AH-receptor (AHR) agonist concentrations of diesel exhaust were lowered by 80-90%, when using the iron- and copper-based DPFs. The tested PAHs accounted for1% of the total AHR-mediated response, indicating that considerable amounts of other aryl hydrocarbons must be present in filtered and unfiltered exhaust. We conclude that both DPFs detoxified diesel exhaust with respect to total aryl hydrocarbons, including the investigated carcinogenic PAHs, but we also noticed a secondary formation of selected nitro-PAHs. Nitration reactions were found to be stereoselective with a preferential substitution of hydrogen atoms at peri-positions. The stereoisomers obtained are related to combustion chemistry, but differ from those formed upon atmospheric nitration of PAHs.

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.

Potential risks of a secondary formation of polychlorinated dibenzodioxins/furans (PCDD/Fs) were assessed for two cordierite-based, wall-through diesel particulate filters (DPFs) for which soot combustion was either catalyzed with an iron- or a copper-based fuel additive. A heavy duty diesel engine was used as test platform, applying the eight-stage ISO 8178/4 C1 cycle. DPF applications neither affected the engine performance, nor did they increase NO, NO2, CO, and CO2 emissions. The latter is a metric for fuel consumption. THC emissions decreased by about 40% when deploying DPFs. PCDD/F emissions, with a focus on tetra- to octachlorinated congeners, were compared under standard and worst case conditions (enhanced chlorine uptake). The iron-catalyzed DPF neither increased PCDD/F emissions, nor did it change the congener pattern, even when traces of chlorine became available. In case of copper, PCDD/F emissions increased by up to 3 orders of magnitude from 22 to 200 to 12 700 pg I-TEQ/L with fuels of2, 14, and 110 microg/g chlorine, respectively. Mainly lower chlorinated DD/Fs were formed. Based on these substantial effects on PCDD/F emissions, the copper-catalyzed DPF system was not approved for workplace applications, whereas the iron system fulfilled all the specifications of the Swiss procedures for DPF approval (VERT).