The application of profluorescent nitroxides to detect reactive oxygen species derived from combustion-generated particulate matter: Cigarette smoke – A case study

Reactive oxygen species (ROS) and related free radicals are considered to be key factors underpinning the various adverse health effects associated with exposure to ambient particulate matter. Therefore, measurement of ROS is a crucial factor for assessing the potential toxicity of particles. In this work, a novel profluorescent nitroxide, BPEAnit, was investigated as a probe for detecting particle-derived ROS. BPEAnit has a very low fluorescence emission due to inherent quenching by the nitroxide group, but upon radical trapping or redox activity, a strong fluorescence is observed. BPEAnit was tested for detection of ROS present in mainstream and sidestream cigarette smoke. In the case of mainstream cigarette smoke, there was a linear increase in fluorescence intensity with an increasing number of cigarette puffs, equivalent to an average of 101 nmol ROS per cigarette based on the number of moles of the probe reacted. Sidestream cigarette smoke sampled from an environmental chamber exposed BPEAnit to much lower concentrations of particles, but still resulted in a clearly detectible increase in fluorescence intensity with sampling time. It was calculated that the amount of ROS was equivalent to 50 ± 2 nmol per mg of particulate matter; however, this value decreased with ageing of the particles in the chamber. Overall, BPEAnit was shown to provide a sensitive response related to the oxidative capacity of the particulate matter. These findings present a good basis for employing the new BPEAnit probe for the investigation of particle-related ROS generated from cigarette smoke as well as from other combustion sources.     

Comparison of light absorption and oxidative potential of biodiesel/diesel and chemicals/diesel blends soot particles

Soot particles,mainly coming from fuel combustion,affect climate forcing through absorbing light and also result in adverse human health outcomes.Though biodiesel or additives blending with diesel was considered environmentally friendly,the understanding on absorbing and oxidative capacity of soot emitted from them are still unclear.The watersoluble organic carbon(WSOC) content,surface chemical structure,light absorption and oxidative potential(OP~(DTT)) of soot from biodiesel/diesel and chemicals/diesel blends were investigated utilizing total organic carbon analyzer,X-ray photoelectron spectrometer,ultraviolet–visible spectrophotometry and dithiothreitol(DTT) assay.The differences and correlations between soot properties were statistically analyzed.Chemicals/diesel blends soot owned significantly higher WSOC content,ratio of mass absorbing efficiency(MAE) in250 and 365 nm(E_2/E_3),OP~(DTT),and higher surface carbonyl content.Coconut biodiesel/diesel blends soot contained evidently higher aromatic carbon–oxygen single bond(Ar_C–O)content,and higher MAE365.The individual comparison of biodiesel/diesel blends showed20% coconut biodiesel blend owned the lowest WSOC,E_2/E_3 and OP~(DTT),while highest Ar_C–O and MAE365,representing strongest absorbing properties.Association analysis showed OP~(DTT)was significantly positively correlated with WSOC.Further,the evident negative correlation between MAE365 and OP~(DTT) was observed.Our results showed coconut biodiesel/diesel blends soot induced lower levels of oxidative potential,whereas absorption of light was higher,which have far reaching consequences on climate forcing.Therefore,it is important to evaluate the balance point between light-absorbing properties and oxidative potential,under the wide use of biodiesel.     

Fungal spore fragmentation as a function of airflow rates and fungal generation methods

The aim of this study was to characterise and quantify the fungal fragment propagules derived and released from several fungal species (Penicillium, Aspergillus niger and Cladosporium cladosporioides) using different generation methods and different air velocities over the colonies. Real time fungal spore fragmentation was investigated using an Ultraviolet Aerodynamic Particle Sizer (UVASP) and a Scanning Mobility Particle Sizer (SMPS). The study showed that there were significant differences (p < 0.01) in the fragmentation percentage between different air velocities for the three generation methods, namely the direct, the fan and the fungal spore source strength tester (FSSST) methods. The percentage of fragmentation also proved to be dependent on fungal species. The study found that there was no fragmentation for any of the fungal species at an air velocity ≤0.4 m s^?1 for any method of generation. Fluorescent signals, as well as mathematical determination also showed that the fungal fragments were derived from spores. Correlation analysis showed that the number of released fragments measured by the UVAPS under controlled conditions can be predicted on the basis of the number of spores, for Penicillium and A. niger, but not for C. cladosporioides. The fluorescence percentage of fragment samples was found to be significantly different to that of non-fragment samples (p < 0.0001) and the fragment sample fluorescence was always less than that of the non-fragment samples. Size distribution and concentration of fungal fragment particles were investigated qualitatively and quantitatively, by both UVAPS and SMPS, and it was found that the UVAPS was more sensitive than the SMPS for measuring small sample concentrations, whilethe results obtained from the UVAPS and SMAS were not identical for the same samples.     

Effect of fuel composition and engine operating conditions on polycyclic aromatic hydrocarbon emissions from a fleet of heavy-duty diesel buses

Emissions from 12 in-service heavy-duty buses powered by low- (LSD) and ultra low-sulfur (ULSD) diesel fuels were measured with the aim to characterize the profile of polycyclic aromatic hydrocarbons (PAHs) in the exhaust and to identify the effect of different types of fuels on the emissions. To mimic on-road conditions as much as possible, sampling was conducted on a chassis dynamometer at four driving modes, namely: mode 7 or idle (0% power), mode 11 (25% power), mode 10 (50% power) and mode 8 (100% power). Irrespective of the type of fuel used, naphthalene, acenaphthene, acenaphthylene, anthracene, phenanthrene, fluorene, fluoranthene and pyrene were found to be the dominant PAHs in the exhaust emissions of the buses. However, the PAH composition in the exhausts of ULSD buses were up to 91±6% less than those in the LSD buses. In particular, three- and four-ringed PAHs were more abundant in the later than in the former. Lowering of fuel sulfur content not only reduced PAH emission, but also decreased the benzo(a)pyrene equivalent (BAP_eq) and hence the toxicity of the exhaust. Result from multicriteria decision-making and multivariate data analysis techniques showed that the use of ULSD afforded cleaner exhaust compositions and emissions with characteristics that are distinct from those obtained by the use of LSD.     

Volcanic sulphate and arctic dust plumes over the North Atlantic Ocean

High time resolution aerosol mass spectrometry measurements were conducted during a field campaign at Mace Head Research Station, Ireland, in June 2007. Observations on one particular day of the campaign clearly indicated advection of aerosol from volcanoes and desert plains in Iceland which could be traced with NOAA Hysplit air mass back trajectories and satellite images. In conjunction with this event, elevated levels of sulphate and light absorbing particles were encountered at Mace Head. While sulphate concentration was continuously increasing, nitrate levels remained low indicating no significant contribution from anthropogenic pollutants. Sulphate concentration increased about 3.8 μg m⁻³ in comparison with the background conditions. Corresponding sulphur flux from volcanic emissions was estimated to about 0.3 TgS yr⁻¹, suggesting that a large amount of sulphur released from Icelandic volcanoes may be distributed over distances larger than 1000 km. Overall, our results corroborate that transport of volcanogenic sulphate and dust particles can significantly change the chemical composition, size distribution, and optical properties of aerosol over the North Atlantic Ocean and should be considered accordingly by regional climate models.     

On the efficiency of impingers with fritted nozzle tip for collection of ultrafine particles

The aim of this study was to determine the collection efficiency of ultrafine particles into an impinger fitted with a fritted nozzle tip as a means to increase contact surface area between the aerosol and the liquid. The influence of liquid sampling volume, frit porosity and the nature of the sampling liquid was explored and it was shown that all impact on the collection efficiency of particles smaller than 220 nm. Obtained values for overall collection efficiency were substantially higher (～30–95%) than have been previously reported, mainly due to the high deposition of particles in the fritted nozzle tip, especially in case of finer porosity frits and smaller particles. Values for the capture efficiency of the solvent alone ranged from 20 to 45%, depending on the type and the volume of solvent. Additionally, our results show that airstream dispersion into bubbles improves particle trapping by the liquid and that there is a difference in collection efficiencies based on the nature and volume of the solvent used.