The effect of temperature and water on secondary organic aerosol formation from ozonolysis of limonene, ?³-carene and ?-pinene

International audienceThe effect of reaction temperature and how water vapour influences the formation of secondary organic aerosol (SOA) in ozonolysis of limonene, ?3-carene and ?-pinene, both regarding number and mass of particles, has been investigated by using a laminar flow reactor G-FROST. Experiments with cyclohexane and 2-butanol (~3.5×1014 molecules cm?3) as OH scavengers were compared to experiments without any scavenger. The reactions were conducted in the temperature range between 298 and 243 K, and at relative humidities between <10 and 80%. Results showed that there is still a scavenger effect on number and mass concentrations at low temperatures between experiments with and without OH scavenger. This shows that the OH chemistry is influencing the SOA formation also at these temperatures. The overall temperature dependence on SOA formation is not as strong as expected from the partitioning theory. In some cases there is even a positive temperature dependence that must be related to changes in the chemical mechanism and/or reduced rates of secondary chemistry at low temperatures. The water effect at low temperature could be explained by physical uptake and cluster stabilisation. At higher temperatures, only a physical explanation is not sufficient and the observations are in line with water changing the chemical mechanism or reaction rates. The data presented adds to the understanding of SOA contribution to atmospheric aerosol composition, new particle formation and atmospheric degradation mechanisms

Fluid structure interaction of submerged metallic and composite plates subjected to low velocity impact loading

An instrumented low velocity impact rig has been used to acquire experimental data for impacts in air and underwater for both metallic and composite plates when subjected to a low velocity drop-weight impact with a 2kg steel impactor. Initial impact studies were conducted in air and then repeated for submersed conditions underwater. Experimental results are compared for all tests with numerical solutions and are found to be in good agreement. For underwater impact, the numerical model incorporates the use of a Eulerian formulation for the water with a coupled fluid-structure interaction algorithm. The effect of the water surrounding the target plates was found to reduce the peak accelerations and also reduce the overall impact duration when compared to the same impacts in air. X-Ray imagery of the composite plates also showed visibly reduced damage for the submersed test specimens. This research provides data on the impact response of metallic and composite materials, and validates numerical methodologies for use in future work on fluid-structure interactions which show strong potential for relevant industrial applications

Finite Element Studies of Transient Wave Propagation

The National Bureau of Standards (NBS) has been working to develop a nondestructive test method for heterogenous solids using transient stress waves [1-5]. The method is referred to as the impact-echo method. The technique involves introducing a transient stress pulse into a test object by mechanical impact at a point and measuring the surface displacement caused by the arrival of reflections of the pulse from internal defects and external boundaries. Successful signal interpretation requires an understanding of the nature of transient stress wave propagation in solids containing defects. A primary focus of the NBS program is on using the finite element method to gain this understanding.</p

Cleavage of E-Cadherin Contributes to Defective Barrier Function in Neosquamous Epithelium

After ablation of Barrett’s esophagus (BE), the esophagus heals with neosquamous epithelium (NSE). Despite normal endoscopic appearance, NSE exhibits defective barrier function with similarities to defects noted in the distal esophageal epithelium in patients with gas-troesophageal reflux disease (GERD)

A transition of atmospheric emissions of particles and gases from on-road heavy-duty trucks

The transition, in extent and characteristics, of atmospheric emissions caused by the modernization of the heavy-duty on-road fleet was studied utilizing roadside measurements. Emissions of particle number (PN), particle mass (PM), black carbon (BC), nitrogen oxides (NOx), carbon monoxide (CO), hydrocarbon (HC), particle size distributions, and particle volatility were measured from 556 individual heavy-duty trucks (HDTs). Substantial reductions in PM, BC, NOx, CO, and to a lesser extent PN were observed from Euro III to Euro VI HDTs by 99 %, 98 %, 93 %, and 57 % for the average emission factors of PM, BC, NOx, and CO, respectively. Despite significant total reductions in NOx emissions, the fraction of NO2 in the NOx emissions increased continuously from Euro IV to Euro VI HDTs. Larger data scattering was evident for PN emissions in comparison to solid particle number (SPN) for Euro VI HDTs, indicating a highly variable fraction of volatile particle components. Particle size distributions of Euro III to enhanced environmentally friendly vehicle (EEV) HDTs were bimodal, whereas those of Euro VI HDTs were nucleation mode dominated. High emitters disproportionately contributed to a large fraction of the total emissions with the highest-emitting 10 % of HDTs in each pollutant category being responsible for 65 % of total PM, 70 % of total PN, and 44 % of total NOx emissions. Euro VI HDTs, which accounted for 53 % of total kilometres driven by Swedish HDTs, were estimated to only contribute to 2 %, 6 %, 12 %, and 47 % of PM, BC, NOx, and PN emissions, respectively. A shift to a fleet dominated by Euro VI HDTs would promote a transition of atmospheric emissions towards low PM, BC, NOx, and CO levels. Nonetheless, reducing PN, SPN, and NO2 emissions from Euro VI HDTs is still important to improve air quality in urban environments

The formation, properties and impact of secondary organic aerosol: current and emerging issues

Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed

Multi-generation OH oxidation as a source for highly oxygenated organic molecules from aromatics

Recent studies have recognised highly oxygenated organic molecules (HOMs) in the atmosphere as important in the formation of secondary organic aerosol (SOA). A large number of studies have focused on HOM formation from oxidation of biogenically emitted monoterpenes. However, HOM formation from anthropogenic vapours has so far received much less attention. Previous studies have identified the importance of aromatic volatile organic compounds (VOCs) for SOA formation. In this study, we investigated several aromatic compounds, benzene (C6H6), toluene (C7H8), and naphthalene (C10H8), for their potential to form HOMs upon reaction with hydroxyl radicals (OH). We performed flow tube experiments with all three VOCs and focused in detail on benzene HOM formation in the Julich Plant Atmosphere Chamber (JPAC). In JPAC, we also investigated the response of HOMs to NOx and seed aerosol. Using a nitrate-based chemical ionisation mass spectrometer (CI-APi-TOF), we observed the formation of HOMs in the flow reactor oxidation of benzene from the first OH attack. However, in the oxidation of toluene and naphthalene, which were injected at lower concentrations, multi-generation OH oxidation seemed to impact the HOM composition. We tested this in more detail for the benzene system in the JPAC, which allowed for studying longer residence times. The results showed that the apparent molar benzene HOM yield under our experimental conditions varied from 4.1% to 14.0%, with a strong dependence on the OH concentration, indicating that the majority of observed HOMs formed through multiple OH-oxidation steps. The composition of the identified HOMs in the mass spectrum also supported this hypothesis. By injecting only phenol into the chamber, we found that phenol oxidation cannot be solely responsible for the observed HOMs in benzene experiments. When NOx was added to the chamber, HOM composition changed and many oxygenated nitrogen-containing products were observed in CI-APi-TOF. Upon seed aerosol injection, the HOM loss rate was higher than predicted by irreversible condensation, suggesting that some undetected oxygenated intermediates also condensed onto seed aerosol, which is in line with the hypothesis that some of the HOMs were formed in multi-generation OH oxidation. Based on our results, we conclude that HOM yield and composition in aromatic systems strongly depend on OH and VOC concentration and more studies are needed to fully understand this effect on the formation of HOMs and, consequently, SOA. We also suggest that the dependence of HOM yield on chamber conditions may explain part of the variability in SOA yields reported in the literature and strongly advise monitoring HOMs in future SOA studies.Peer reviewe

Evolution of the complex refractive index in the UV spectral region in ageing secondary organic aerosol

The chemical and physical properties of secondary organic aerosol (SOA) formed by the photochemical degradation of biogenic and anthropogenic volatile organic compounds (VOC) are as yet still poorly constrained. The evolution of the complex refractive index (RI) of SOA, formed from purely biogenic VOC and mixtures of biogenic and anthropogenic VOC, was studied over a diurnal cycle in the SAPHIR photochemical outdoor chamber in Jülich, Germany. The correlation of RI with SOA chemical and physical properties such as oxidation level and volatility was examined. The RI was retrieved by a newly developed broadband cavity-enhanced spectrometer for aerosol optical extinction measurements in the UV spectral region (360 to 420 nm). Chemical composition and volatility of the particles were monitored by a high-resolution time-of-flight aerosol mass spectrometer, and a volatility tandem differential mobility analyzer. SOA was formed by ozonolysis of either (i) a mixture of biogenic VOC (α-pinene and limonene), (ii) biogenic VOC mixture with subsequent addition of an anthropogenic VOC (<i>p</i>-xylene-d₁₀), or (iii) a mixture of biogenic and anthropogenic VOC. The SOA aged by ozone/OH reactions up to 29.5 h was found to be non-absorbing in all cases. The SOA with <i>p</i>-xylene-d₁₀ showed an increase of the scattering component of the RI correlated with an increase of the O / C ratio and with an increase in the SOA density. There was a greater increase in the scattering component of the RI when the SOA was produced from the mixture of biogenic VOCs and anthropogenic VOC than from the sequential addition of the VOCs after approximately the same ageing time. The increase of the scattering component was inversely correlated with the SOA volatility. Two RI retrievals determined for the pure biogenic SOA showed a constant RI for up to 5 h of ageing. Mass spectral characterization shows the three types of the SOA formed in this study have a significant amount of semivolatile components. The influence of anthropogenic VOCs on the oxygenated organic aerosol as well as the atmospheric implications are discussed