Direct field evidence of autocatalytic iodine release from atmospheric aerosol.

Reactive iodine plays a key role in determining the oxidation capacity, or cleansing capacity, of the atmosphere in addition to being implicated in the formation of new particles in the marine boundary layer. The postulation that heterogeneous cycling of reactive iodine on aerosols may significantly influence the lifetime of ozone in the troposphere not only remains poorly understood but also heretofore has never been observed or quantified in the field. Here, we report direct ambient observations of hypoiodous acid (HOI) and heterogeneous recycling of interhalogen product species (i.e., iodine monochloride [ICl] and iodine monobromide [IBr]) in a midlatitude coastal environment. Significant levels of ICl and IBr with mean daily maxima of 4.3 and 3.0 parts per trillion by volume (1-min average), respectively, have been observed throughout the campaign. We show that the heterogeneous reaction of HOI on marine aerosol and subsequent production of iodine interhalogens are much faster than previously thought. These results indicate that the fast formation of iodine interhalogens, together with their rapid photolysis, results in more efficient recycling of atomic iodine than currently considered in models. Photolysis of the observed ICl and IBr leads to a 32% increase in the daytime average of atomic iodine production rate, thereby enhancing the average daytime iodine-catalyzed ozone loss rate by 10 to 20%. Our findings provide direct field evidence that the autocatalytic mechanism of iodine release from marine aerosol is important in the atmosphere and can have significant impacts on atmospheric oxidation capacity.

Toward Rigorous Materials Production: New Approach Methodologies Have Extensive Potential to Improve Current Safety Assessment Practices.

Advanced material development, including at the nanoscale, comprises costly and complex challenges coupled to ensuring human and environmental safety. Governmental agencies regulating safety have announced interest toward acceptance of safety data generated under the collective term New Approach Methodologies (NAMs), as such technologies/approaches offer marked potential to progress the integration of safety testing measures during innovation from idea to product launch of nanomaterials. Divided in overall eight main categories, searchable databases for grouping and read across purposes, exposure assessment and modeling, in silico modeling of physicochemical structure and hazard data, in vitro high-throughput and high-content screening assays, dose-response assessments and modeling, analyses of biological processes and toxicity pathways, kinetics and dose extrapolation, consideration of relevant exposure levels and biomarker endpoints typify such useful NAMs. Their application generally agrees with articulated stakeholder needs for improvement of safety testing procedures. They further fit for inclusion and add value in nanomaterials risk assessment tools. Overall 37 of 50 evaluated NAMs and tiered workflows applying NAMs are recommended for considering safer-by-design innovation, including guidance to the selection of specific NAMs in the eight categories. An innovation funnel enriched with safety methods is ultimately proposed under the central aim of promoting rigorous nanomaterials innovation.

Traffic is a major source of atmospheric nanocluster aerosol.

In densely populated areas, traffic is a significant source of atmospheric aerosol particles. Owing to their small size and complicated chemical and physical characteristics, atmospheric particles resulting from traffic emissions pose a significant risk to human health and also contribute to anthropogenic forcing of climate. Previous research has established that vehicles directly emit primary aerosol particles and also contribute to secondary aerosol particle formation by emitting aerosol precursors. Here, we extend the urban atmospheric aerosol characterization to cover nanocluster aerosol (NCA) particles and show that a major fraction of particles emitted by road transportation are in a previously unmeasured size range of 1.3-3.0 nm. For instance, in a semiurban roadside environment, the NCA represented 20-54% of the total particle concentration in ambient air. The observed NCA concentrations varied significantly depending on the traffic rate and wind direction. The emission factors of NCA for traffic were 2.4·1015 (kgfuel)-1 in a roadside environment, 2.6·1015 (kgfuel)-1 in a street canyon, and 2.9·1015 (kgfuel)-1 in an on-road study throughout Europe. Interestingly, these emissions were not associated with all vehicles. In engine laboratory experiments, the emission factor of exhaust NCA varied from a relatively low value of 1.6·1012 (kgfuel)-1 to a high value of 4.3·1015 (kgfuel)-1 These NCA emissions directly affect particle concentrations and human exposure to nanosized aerosol in urban areas, and potentially may act as nanosized condensation nuclei for the condensation of atmospheric low-volatile organic compounds.

Nanocluster Aerosol Emissions of a 3D Printer.

Many studies exist that characterize the aerosol emissions from fused filament fabrication three-dimensional (3D) printers. However, nanocluster aerosol (NCA) particles, that is particles in a size range under 3 nm, are rarely studied. The purpose of this study was to characterize the NCA emissions and the contribution of NCA to the total particle number emissions from a 3D printer. We used a particle size magnifier and a scanning mobility particle sizer to measure the time evolution of particle size distribution, which was used to calculate the average NCA emission rates during a printer operation in a chamber. The NCA emission rates ranged from 1.4 × 106 to 7.3 × 109 s-1 depending on the applied combination of filament material and nozzle temperature, showing increasing emission with increasing temperature. The NCA emissions constitute from 9 to 48% of the total emissions, that is, almost half of the particle emissions may have been previously neglected. Therefore, it is essential to include the low NCA size range in, for example, future 3D-printer-testing protocols, emission measurement standards, and risk management measures.

Airport emission particles: exposure characterization and toxicity following intratracheal instillation in mice.

BACKGROUND: Little is known about the exposure levels and adverse health effects of occupational exposure to airplane emissions. Diesel exhaust particles are classified as carcinogenic to humans and jet engines produce potentially similar soot particles. Here, we evaluated the potential occupational exposure risk by analyzing particles from a non-commercial airfield and from the apron of a commercial airport. Toxicity of the collected particles was evaluated alongside NIST standard reference diesel exhaust particles (NIST2975) in terms of acute phase response, pulmonary inflammation, and genotoxicity after single intratracheal instillation in mice. RESULTS: Particle exposure levels were up to 1 mg/m3 at the non-commercial airfield. Particulate matter from the non-commercial airfield air consisted of primary and aggregated soot particles, whereas commercial airport sampling resulted in a more heterogeneous mixture of organic compounds including salt, pollen and soot, reflecting the complex occupational exposure at an apron. The particle contents of polycyclic aromatic hydrocarbons and metals were similar to the content in NIST2975. Mice were exposed to doses 6, 18 and 54 µg alongside carbon black (Printex 90) and NIST2975 and euthanized after 1, 28 or 90 days. Dose-dependent increases in total number of cells, neutrophils, and eosinophils in bronchoalveolar lavage fluid were observed on day 1 post-exposure for all particles. Lymphocytes were increased for all four particle types on 28 days post-exposure as well as for neutrophil influx for jet engine particles and carbon black nanoparticles. Increased Saa3 mRNA levels in lung tissue and increased SAA3 protein levels in plasma were observed on day 1 post-exposure. Increased levels of DNA strand breaks in bronchoalveolar lavage cells and liver tissue were observed for both particles, at single dose levels across doses and time points. CONCLUSIONS: Pulmonary exposure of mice to particles collected at two airports induced acute phase response, inflammation, and genotoxicity similar to standard diesel exhaust particles and carbon black nanoparticles, suggesting similar physicochemical properties and toxicity of jet engine particles and diesel exhaust particles. Given this resemblance as well as the dose-response relationship between diesel exhaust exposure and lung cancer, occupational exposure to jet engine emissions at the two airports should be minimized.

New particle formation in forests inhibited by isoprene emissions.

It has been suggested that volatile organic compounds (VOCs) are involved in organic aerosol formation, which in turn affects radiative forcing and climate. The most abundant VOCs emitted by terrestrial vegetation are isoprene and its derivatives, such as monoterpenes and sesquiterpenes. New particle formation in boreal regions is related to monoterpene emissions and causes an estimated negative radiative forcing of about -0.2 to -0.9 W m(-2). The annual variation in aerosol growth rates during particle nucleation events correlates with the seasonality of monoterpene emissions of the local vegetation, with a maximum during summer. The frequency of nucleation events peaks, however, in spring and autumn. Here we present evidence from simulation experiments conducted in a plant chamber that isoprene can significantly inhibit new particle formation. The process leading to the observed decrease in particle number concentration is linked to the high reactivity of isoprene with the hydroxyl radical (OH). The suppression is stronger with higher concentrations of isoprene, but with little dependence on the specific VOC mixture emitted by trees. A parameterization of the observed suppression factor as a function of isoprene concentration suggests that the number of new particles produced depends on the OH concentration and VOCs involved in the production of new particles undergo three to four steps of oxidation by OH. Our measurements simulate conditions that are typical for forested regions and may explain the observed seasonality in the frequency of aerosol nucleation events, with a lower number of nucleation events during summer compared to autumn and spring. Biogenic emissions of isoprene are controlled by temperature and light, and if the relative isoprene abundance of biogenic VOC emissions increases in response to climate change or land use change, the new particle formation potential may decrease, thus damping the aerosol negative radiative forcing effect.

Comparison of dust release from epoxy and paint nanocomposites and conventional products during sanding and sawing.

The release of dust generated during sanding or sawing of nanocomposites was compared with conventional products without nanomaterials. Epoxy-based polymers with and without carbon nanotubes, and paints with different amounts of nano-sized titanium dioxide, were machined in a closed aerosol chamber. The temporal evolution of the aerosol concentration and size distribution were measured simultaneously. The morphology of collected dust by scanning electron microscopy was different depending on the type of nanocomposites: particles from carbon nanotubes (CNTs) nanocomposites had protrusions on their surfaces and aggregates and agglomerates are attached to the paint matrix in particles emitted from alkyd paints. We observed no significant differences in the particle size distributions when comparing sanding dust from nanofiller containing products with dust from conventional products. Neither did we observe release of free nanomaterials. Instead, the nanomaterials were enclosed or partly enclosed in the matrix. A source strength term Si (cm(-3) s(-1)) that describes particle emission rates from continuous sources was introduced. Comparison between the Si parameters derived from sanding different materials allows identification of potential effects of addition of engineered nanoparticles to a composite.

Local Scale Exposure and Fate of Engineered Nanomaterials.

Nanotechnology is a growing megatrend in industrial production and innovations. Many applications utilize engineered nanomaterials (ENMs) that are potentially released into the atmospheric environment, e.g., via direct stack emissions from production facilities. Limited information exists on adverse effects such ENM releases may have on human health and the environment. Previous exposure modeling approaches have focused on large regional compartments, into which the released ENMs are evenly mixed. However, due to the localization of the ENM release and removal processes, potentially higher airborne concentrations and deposition fluxes are obtained around the production facilities. Therefore, we compare the ENM concentrations from a dispersion model to those from the uniformly mixed compartment approach. For realistic release scenarios, we based the modeling on the case study measurement data from two TiO2 nanomaterial handling facilities. In addition, we calculated the distances, at which 50% of the ENMs are deposited, serving as a physically relevant metric to separate the local scale from the regional scale, thus indicating the size of the high exposure and risk region near the facility. As a result, we suggest a local scale compartment to be implemented in the multicompartment nanomaterial exposure models. We also present a computational tool for local exposure assessment that could be included to regulatory guidance and existing risk governance networks.

Particle emissions of Euro VI, EEV and retrofitted EEV city buses in real traffic.

Exhaust emissions from traffic significantly affect urban air quality. In this study, in-traffic emissions of diesel-fueled city buses meeting enhanced environmentally friendly vehicle (EEV) and Euro VI emission limits and the effects of retrofitting of EEV buses were studied on-road by chasing the buses with a mobile laboratory in the Helsinki region, Finland. The average emission factors of particle number (PN), particle mass (PM1) and black carbon mass (BC) were 0.86·1015 1/kgfuel, 0.20 g/kgfuel and 0.10 g/kgfuel, respectively, for EEV buses. For Euro VI buses, the emissions were below 0.5·1015 1/kgfuel (PN), 0.07 g/kgfuel (PM1) and 0.02 g/kgfuel (BC), and the exhaust plume concentrations of these pollutants were close to the background concentrations. The emission factors of PM1 and BC of retrofitted EEV buses were at the level of Euro VI buses, but their particle number emissions varied significantly. On average, the EEV buses were observed to emit the largest amounts of nanocluster aerosol (NCA) (i.e., the particles with size between 1.3 and 3 nm). High NCA emissions were linked with high PN emissions. In general, results demonstrate that advanced exhaust aftertreatment systems reduce emissions of larger soot particles but not small nucleation mode particles in all cases.

Characterization of laboratory and real driving emissions of individual Euro 6 light-duty vehicles - Fresh particles and secondary aerosol formation.

Emissions from passenger cars are one of major sources that deteriorate urban air quality. This study presents characterization of real-drive emissions from three Euro 6 emission level passenger cars (two gasoline and one diesel) in terms of fresh particles and secondary aerosol formation. The gasoline vehicles were also characterized by chassis dynamometer studies. In the real-drive study, the particle number emissions during regular driving were 1.1-12.7 times greater than observed in the laboratory tests (4.8 times greater on average), which may be caused by more effective nucleation process when diluted by real polluted and humid ambient air. However, the emission factors measured in laboratory were still much higher than the regulatory value of 6 × 1011 particles km-1. The higher emission factors measured here result probably from the fact that the regulatory limit considers only non-volatile particles larger than 23 nm, whereas here, all particles (also volatile) larger than 3 nm were measured. Secondary aerosol formation potential was the highest after a vehicle cold start when most of the secondary mass was organics. After the cold start, the relative contributions of ammonium, sulfate and nitrate increased. Using a novel approach to study secondary aerosol formation under real-drive conditions with the chase method resulted mostly in emission factors below detection limit, which was not in disagreement with the laboratory findings.

Vertical profiles of lung deposited surface area concentration of particulate matter measured with a drone in a street canyon.

The vertical profiles of lung deposited surface area (LDSA) concentration were measured in an urban street canyon in Helsinki, Finland, by using an unmanned aerial system (UAS) as a moving measurement platform. The street canyon can be classified as an avenue canyon with an aspect ratio of 0.45 and the UAS was a multirotor drone especially modified for emission measurements. In the experiments of this study, the drone was equipped with a small diffusion charge sensor capable of measuring the alveolar LDSA concentration of particles. The drone measurements were conducted during two days on the same spatial location at the kerbside of the street canyon by flying vertically from the ground level up to an altitude of 50 m clearly above the rooftop level (19 m) of the nearest buildings. The drone data were supported by simultaneous measurements and by a two-week period of measurements at nearby locations with various instruments. The results showed that the averaged LDSA concentrations decreased approximately from 60 µm2/cm3 measured close to the ground level to 36-40 µm2/cm3 measured close to the rooftop level of the street canyon, and further to 16-26 µm2/cm3 measured at 50 m. The high-resolution measurement data enabled an accurate analysis of the functional form of vertical profiles both in the street canyon and above the rooftop level. In both of these regions, exponential fits were used and the parameters obtained from the fits were thoroughly compared to the values found in literature. The results of this study indicated that the role of turbulent mixing caused by traffic was emphasized compared to the street canyon vortex as a driving force of the dispersion. In addition, the vertical profiles above the rooftop level showed a similar exponential decay compared to the profiles measured inside the street canyon.

Measurement of the nucleation of atmospheric aerosol particles.

The formation of new atmospheric aerosol particles and their subsequent growth have been observed frequently at various locations all over the world. The atmospheric nucleation rate (or formation rate) and growth rate (GR) are key parameters to characterize the phenomenon. Recent progress in measurement techniques enables us to measure atmospheric nucleation at the size (mobility diameter) of 1.5 (±0.4) nm. The detection limit has decreased from 3 to 1 nm within the past 10 years. In this protocol, we describe the procedures for identifying new-particle-formation (NPF) events, and for determining the nucleation, formation and growth rates during such events under atmospheric conditions. We describe the present instrumentation, best practices and other tools used to investigate atmospheric nucleation and NPF at a certain mobility diameter (1.5, 2.0 or 3.0 nm). The key instruments comprise devices capable of measuring the number concentration of the formed nanoparticles and their size, such as a suite of modern condensation particle counters (CPCs) and air ion spectrometers, and devices for characterizing the pre-existing particle number concentration distribution, such as a differential mobility particle sizer (DMPS). We also discuss the reliability of the methods used and requirements for proper measurements and data analysis. The time scale for realizing this procedure is 1 year.