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Waste incineration had been identified as an important source of ultrafine air pollutants resulting in elaborated treatment systems for exhaust air. Nowadays, these systems are able to remove almost all ultrafine particles. However, the fate of ultrafine particles caught in the filters has received little attention so far. Based on the use of engineered nano-objects (ENO) and their transfer into the waste stream, it can be expected that not only combustion generated nanoparticles are found in fly ashes but that many ENO finally end up in this matrix. A more detailed characterization of the nanoparticulate fraction of fly ashes is therefore needed. Physical and chemical characterizations were performed for fly ashes from five selected waste incineration plants (WIPs) with different input materials such as municipal waste, wood and sewage sludge. The intrinsic densities of the fly ashes were in the range of 2.7-3.2 g/cm(3). When the fly ash particle became airborne, the effective density depended on the particle size, increasing from 0.7-0.8 g/cm(3) for 100-150 nm to 2 g/cm(3) for 350-500 nm. The fly ash samples were fractionated at 2 µm, yielding fine fractions (<2 µm) and coarse fractions (>2 µm). The size distributions of the fine fractions in the airborne form were further characterized, which allowed calculation of the percentage of the fly ash particles below 100 nm. We found the highest mass-based percentage was about 0.07%; the number percentage in the fine fraction was in the range of 4.8% to 22%. Comparison with modeling results showed that ENO may constitute a considerable part of the fly ash particles below 100 nm. Chemical analyses showed that for the municipal waste samples Ca and Al were present in higher concentrations in the coarse fraction; for the mixed wood and sludge sample the P concentration was higher in the coarse fraction; for most other samples and elements they were enriched in the fine fraction. Electron microscopic images of fly ashes showed a wide range of particle sizes, from nanometer range to micrometer range. Many aggregated particles were observed, demonstrating that ENO, bulk-derived nano-objects and combustion-generated nano-objects can form aggregates in the incineration process.
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Ceniza del Carbón/química , Incineración , Material Particulado/análisis , Administración de Residuos/métodos , Microscopía Electrónica de Rastreo , Microscopía Electrónica de Transmisión , Tamaño de la Partícula , Aguas del Alcantarillado , Residuos Sólidos , Espectrometría por Rayos X , Suiza , MaderaRESUMEN
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.
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Nanopartículas/química , Pintura/análisis , Titanio/química , Humanos , Luz , Nanopartículas/ultraestructura , Tamaño de la Partícula , Material Particulado/análisis , Polvos , Dispersión de Radiación , Electricidad Estática , Agua/químicaRESUMEN
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.
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Aerosoles/efectos adversos , Exposición por Inhalación/análisis , Nanopartículas/efectos adversos , Humanos , Modelos Teóricos , Tamaño de la Partícula , Plaguicidas/análisisRESUMEN
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.
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Filtración/métodos , Hierro/química , Dibenzodioxinas Policloradas/análogos & derivados , Potasio/química , Benzofuranos , Catálisis , Dibenzodioxinas Policloradas/químicaRESUMEN
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.
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Filtración/instrumentación , Gasolina/análisis , Nitratos/análisis , Nitritos/análisis , Material Particulado/química , Especies de Nitrógeno Reactivo/análisis , Emisiones de Vehículos/análisis , Catálisis , Ambiente , Óxido Nítrico/análisis , Temperatura , Factores de Tiempo , Torque , Urea/químicaRESUMEN
The European Union has been concerned about cadmium (Cd), because of its toxic nature, since the 1970s. While many anthropogenic sources of Cd were regulated early on at the community level, and most member states later established national limits, Cd content in widely used mineral fertilizers remains uncontrolled across the EU. In 1997, the European Commission first suggested phased Cd limit values in mineral fertilizers as a promising approach to reducing Cd content in soils and harmonising national measures. For over 20â¯years, however, no harmonised measures have been adopted because confusion remains about the basis for, and level of, such limits. We comment on the latest deadlock over the revision of the Fertilisers Regulation and strengthen assumptions as to why such limits are timely, pertinent, and possible.
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Mineral phosphorus (P) fertilizers contain contaminants that are potentially hazardous to humans and the environment. Frequent mineral P fertilizer applications can cause heavy metals to accumulate and reach undesirable concentrations in agricultural soils. There is particular concern about Cadmium (Cd) and Uranium (U) accumulation because these metals are toxic and can endanger soil fertility, leach into groundwater, and be taken up by crops. We determined total Cd and U concentrations in more than 400 topsoil and subsoil samples obtained from 216 agricultural sites across Switzerland. We also investigated temporal changes in Cd and U concentrations since 1985 in soil at six selected Swiss national soil monitoring network sites. The mean U concentrations were 16% higher in arable topsoil than in grassland topsoil. The Cd concentrations in arable and grassland soils did not differ, which we attribute to soil management practices and Cd sources other than mineral P fertilizers masking Cd inputs from mineral P fertilizers. The mean Cd and U concentrations were 58% and 9% higher, respectively, in arable topsoil than in arable subsoil, indicating that significant Cd and U inputs to arable soils occurred in the past. Geochemical mass balances confirmed this, indicating an accumulation of 52% for Cd and 6% for U. Only minor temporal changes were found in the Cd concentrations in topsoil from the six soil-monitoring sites, but U concentrations in topsoil from three sites had significantly increased since 1985. Sewage sludge and atmospheric deposition were previously important sources of Cd to agricultural soils, but today mineral P fertilizers are the dominant sources of Cd and U. Future Cd and U inputs to agricultural soils may be reduced by using optimized management practices, establishing U threshold values for mineral P fertilizers and soils, effectively enforcing threshold values, and developing and using clean recycled P fertilizers.
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Cadmio/análisis , Monitoreo del Ambiente , Contaminantes del Suelo/análisis , Suelo/química , Uranio/análisis , Agricultura , Productos Agrícolas , Fertilizantes/análisis , Fósforo , Aguas del Alcantarillado , SuizaRESUMEN
Intensification of agricultural production worldwide has altered cycles of phosphorus (P) and water. In particular, loading of P on land in fertilizer applications is a global water quality concern. The Lake Winnipeg Basin (LWB) is a major agricultural area displaying extreme eutrophication. We examined the eutrophication problem in the context of the reemerging global concern about future accessibility of phosphate rock for fertilizer production and sustainable phosphorus management. An exploratory action research participatory design was applied to study options for proactivity within the LWB. The multiple methods, including stakeholder interviews and surveys, demonstrate emerging synergies between the goals of reversing eutrophication and promoting food security. Furthermore, shifting the prevalent pollutant-driven eutrophication management paradigm in the basin toward a systemic, holistic and ecocentric approach, integrating global resource challenges, requires a mutual learning process among stakeholders in the basin to act on and adapt to ecosystem vulnerabilities. It is suggested to continue aspects of this research in a transdisciplinary format, i.e., science with society, in response to globally-expanding needs and concerns, with a possible focus on enhanced engagement of indigenous peoples and elders.
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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.
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Nanoestructuras/análisis , Pintura , Dióxido de Silicio/análisis , Rayos Ultravioleta , Contaminantes Químicos del Agua/análisis , Agua/química , Nanoestructuras/química , Pintura/efectos de la radiación , Dióxido de Silicio/química , Contaminantes Químicos del Agua/químicaRESUMEN
Despite evidence against imminent global phosphate rock depletion, phosphorus (P) scarcity scenarios and the subsequent consequences for global food security continue to be a matter of controversy. We provide a historicizing account to evaluate the degree and relevance of past human experiences with P scarcity. Using more than 80 literature sources, we trace the origin of the P scarcity concept and the first accounts of concerns; we report on three cases of scarcity discourse in the U.S. and revisit the concept of future resources. In addition, we present past evaluations of phosphate rock reserves and lifetime estimates for the world, the U.S., Morocco, and the Western Sahara, as well as past attempts to model phosphorus supply or collect information on phosphate rock. Our results show that current concerns have a long legacy and knowledge base to draw from and that promulgating the notion of depletion is inconsistent with past findings. We find that past depletion concerns were refuted by means of new resource appraisals, indicating that the supply was substantially larger than previously thought. Moreover, recommendations for national P conservation policies and other practices seem to have found little implementation. We demonstrate the merit of historic literacy for social learning and the weakness of the current P sustainability debate because it does not include this past knowledge.
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Conservación de los Recursos Naturales , Fósforo , Agricultura , Marruecos , Estados UnidosRESUMEN
This study seeks to identify and specify the components that make up the prospects of U recovery from phosphate rock. A systems approach is taken. The assessment includes i) reviewing past recovery experience and lessons learned; ii) identifying factors that determine recovery; and iii) establishing a contemporary evaluation of U endowments in phosphate rock reserves, as well as the available and recoverable amounts from phosphate rock and phosphoric acid production. We find that in the past, recovery did not fulfill its potential and that the breakup of the Soviet Union worsened then-favorable recovery market conditions in the 1990s. We find that an estimated 5.7 million tU may be recoverable from phosphate rock reserves. In 2010, the recoverable tU from phosphate rock and phosphoric acid production may have been 15,000 tU and 11,000 tU, respectively. This could have filled the world U supply-demand gap for nuclear energy production. The results suggest that the U.S., Morocco, Tunisia, and Russia would be particularly well-suited to recover U, taking infrastructural considerations into account. We demonstrate future research needs, as well as sustainability orientations. We conclude that in order to promote investment and production, it seems necessary to establish long-term contracts at guaranteed prices, ensuring profitability for phosphoric acid producers.
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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.
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Fraccionamiento de Campo-Flujo/métodos , Nanopartículas del Metal/química , Titanio/química , Tamaño de la PartículaRESUMEN
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.
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Desinfectantes/toxicidad , Nanopartículas del Metal/toxicidad , Plata/análisis , Ambiente , Iones , Nanopartículas del Metal/química , Modelos Químicos , Medición de Riesgo , Plata/química , Plata/toxicidad , Tiempo (Meteorología) , MaderaRESUMEN
Phosphorus is an essential element of life and of the modern agricultural system. Today, science, policy, agro-industry and other stakeholder groups are increasingly concerned about the sustainable use of this resource, given the dissipative nature of phosphorus and difficulties in assessing, evaluating, and coping with phosphorus pollution in aquatic and terrestrial systems. We argue that predictions about a forthcoming peak, followed by a quick reduction (i.e., physical phosphate rock scarcity) are unreasoned and stress that access to phosphorus (economic scarcity) is already, and may increasingly become critical, in particular for smallholders farmers in different parts of the world. The paper elaborates on the design, development, goals and cutting-edge contributions of a global transdisciplinary process (i.e. mutual learning between science and society including multiple stakeholders) on the understanding of potential contributions and risks related to the current mode of using phosphorus on multiple scales (Global TraPs). While taking a global and comprehensive view on the whole phosphorus-supply chain, Global TraPs organizes and integrates multiple transdisciplinary case studies to better answer questions which inform sustainable future phosphorus use. Its major goals are to contribute to four issues central to sustainable resource management: i) long-term management of biogeochemical cycles, in particular the challenge of closing the phosphorus cycle, ii) achieving food security, iii) avoiding environmental pollution and iv) sustainability learning on a global level by transdisciplinary processes.
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Agricultura/métodos , Conservación de los Recursos Naturales/economía , Conservación de los Recursos Naturales/métodos , Fertilizantes/análisis , Fósforo/química , Agricultura/economía , Agricultura/tendencias , Abastecimiento de Alimentos/métodos , Comunicación Interdisciplinaria , Cooperación InternacionalRESUMEN
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.
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Monitoreo del Ambiente , Contaminantes Ambientales/análisis , Modelos Químicos , Nanoestructuras/análisis , Eliminación de ResiduosRESUMEN
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.
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Nanopartículas/análisis , Pintura , Titanio/análisis , Contaminantes Químicos del Agua/análisis , Ambiente Controlado , Microscopía Electrónica de RastreoRESUMEN
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.
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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.
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Contaminantes Atmosféricos/química , Filtración/instrumentación , Mutágenos/química , Emisiones de Vehículos/análisis , Estructura Molecular , Oxidación-Reducción , OxígenoRESUMEN
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 for < 1% 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.