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The concentration, nature, and persistence of particulate matter (PM)-bound reactive oxygen species (ROS) are of significant interest in understanding how atmospheric pollution affects health. However, the inherent difficulties in their measurement, particularly regarding the so-called "short-lived" ROS, have limited our understanding of their persistence and concentrations in the atmosphere. This paper aims to address this limitation through the analysis of PM-bound ROS measurements from the Particle Into Nitroxide Quencher (PINQ) system at an atmospheric monitoring site in the city of Heshan, Guangdong Province, China. The measured daily average and standard deviation for the measurement period was 0.050 ± 0.017 nmol·m-3. The averaged measured concentration of ROS per mass of PM and standard deviation was 0.0012 ± nmol·mg. The dataset was also correlated with standard pollutants, and a simplified model was constructed to separate the contributions of short-lived (t1/2 = 5 min) and long-lived (t1/2 ∼ infinity) ROS to total concentration using ozone, carbon monoxide, and PM mass. This showed that the short-lived ROS contribute an average of 33% of the daily PM-bound ROS burden over the measurement period, up to 52% of daily average on elevated days, and up to 71% for hourly averages. These results highlight the need for accurate measurements of short-lived ROS and provide the starting point for a general model to predict PM-bound ROS concentrations using widely available standard pollutants for future epidemiological research.

The chemical composition and evolution of secondary organic aerosol (SOA) in the atmosphere represents one of the largest uncertainties in our current understanding of air quality. Despite vast research, the toxicological mechanisms relating to adverse human health effects upon exposure to particulate matter are still poorly understood. Particle-bound reactive oxygen species (ROS) may substantially contribute to observed health effects by influencing aerosol oxidative potential (OP). The role of radicals in both the formation and aging of aerosol, as well as their contribution to aerosol OP, remains highly uncertain. The profluorescent spin trap BPEAnit (9,10-bis(phenylethynyl)anthracenenitroxide), previously utilized to study combustion-generated aerosol, has been applied to provide the first estimate of particle-bound radical concentrations in SOA. We demonstrate that SOA from different atmospherically important VOC precursors have different particle-bound radical concentrations, estimated for the ozonolysis of α-pinene (0.020 ± 0.0050 nmol/μg), limonene (0.0059 ± 0.0010 nmol/μg), and β-caryophyllene (0.0025 ± 0.00080 nmol/μg), highlighting the potential importance of OH-initiated formation of particle-bound organic radicals. Additionally, the lifetime of particle-bound radical species in α-pinene SOA was estimated, and a pseudo-first-order rate constant of k = 7.3 ± 1.7 × 10–3 s–1 was derived, implying a radical lifetime on the order of minutes.

Compression ignition (CI) engine design is subject to many constraints, which present a multicriteria optimization problem that the engine researcher must solve. In particular, the modern CI engine must not only be efficient but must also deliver low gaseous, particulate, and life cycle greenhouse gas emissions so that its impact on urban air quality, human health, and global warming is minimized. Consequently, this study undertakes a multicriteria analysis, which seeks to identify alternative fuels, injection technologies, and combustion strategies that could potentially satisfy these CI engine design constraints. Three data sets are analyzed with the Preference Ranking Organization Method for Enrichment Evaluations and Geometrical Analysis for Interactive Aid (PROMETHEE-GAIA) algorithm to explore the impact of (1) an ethanol fumigation system, (2) alternative fuels (20% biodiesel and synthetic diesel) and alternative injection technologies (mechanical direct injection and common rail injection), and (3) various biodiesel fuels made from 3 feedstocks (i.e., soy, tallow, and canola) tested at several blend percentages (20-100%) on the resulting emissions and efficiency profile of the various test engines. The results show that moderate ethanol substitutions (∼20% by energy) at moderate load, high percentage soy blends (60-100%), and alternative fuels (biodiesel and synthetic diesel) provide an efficiency and emissions profile that yields the most "preferred" solutions to this multicriteria engine design problem. Further research is, however, required to reduce reactive oxygen species (ROS) emissions with alternative fuels and to deliver technologies that do not significantly reduce the median diameter of particle emissions. © 2013 American Chemical Society.

Volatile properties of particle emissions from four compressed natural gas (CNG) and four diesel buses were investigated under steady-state and transient driving modes on a chassis dynamometer. The exhaust was diluted utilizing a full-flow continuous volume sampling system and passed through a thermodenuder at controlled temperature. Particle number concentration and size distribution were measured with a condensation particle counter and a scanning mobility particle sizer, respectively. We show that while almost all the particles emitted by the CNG buses were in the nanoparticle size range, at least 85% and 98% were removed at 100 and 250 °C, respectively. Closer analysis of the volatility of particles emitted during transient cycles showed that volatilization began at around 40 °C, with the majority occurring by 80 °C. Particles produced during hard acceleration from rest exhibited lower volatility than those produced during other times of the cycle. On the basis of our results and the observation of ash deposits on the walls of the tailpipes, we suggest that these nonvolatile particles were composed mostly of ash from lubricating oil. Heating the diesel bus emissions to 100 °C removed ultrafine particle numbers by 69-82% when a nucleation mode was present and just 18% when it was not.

Alternative fuels and injection technologies are a necessary component of particulate emission reduction strategies for compression ignition engines. Consequently, this study undertakes a physicochemical characterization of diesel particulate matter (DPM) for engines equipped with alternative injection technologies (direct injection and common rail) and alternative fuels (ultra low sulfur diesel, a 20% biodiesel blend, and a synthetic diesel). Particle physical properties were addressed by measuring particle number size distributions, and particle chemical properties were addressed by measuring polycyclic aromatic hydrocarbons (PAHs) and reactive oxygen species (ROS). Particle volatility was determined by passing the polydisperse size distribution through a thermodenuder set to 300 °C. The results from this study, conducted over a four point test cycle, showed that both fuel type and injection technology have an impact on particle emissions, but injection technology was the more important factor. Significant particle number emission (54%-84%) reductions were achieved at half load operation (1% increase-43% decrease at full load) with the common rail injection system; however, the particles had a significantly higher PAH fraction (by a factor of 2 to 4) and ROS concentrations (by a factor of 6 to 16) both expressed on a test-cycle averaged basis. The results of this study have significant implications for the health effects of DPM emissions from both direct injection and common rail engines utilizing various alternative fuels. © 2011 American Chemical Society.

The volatile and hygroscopic properties of diesel nanoparticles were simultaneously determined under a range of engine loads using the volatilization and humidification tandem differential mobility analyzer (VH-TDMA). Additionally, the VH-TDMA was used to measure changes in the hygroscopic behavior of the heterogeneously nucleated diesel nanoparticles as one or more semivolatile species were removed via thermal evaporation or decomposition. Particles produced at high loads exhibited high, dual-step volatility, while those particles produced at low loads were less volatile and exhibited continuous volatilization curves. The hygroscopic growth factor of the particles was shown to be load dependent with high-load particles exhibiting growth factors similar to that of ammonium sulfate. At 85% relative humidity, particles produced at moderate loads exhibited growth factors of approximately 1.1 while low-load particles were shown to be hydrophobic. Growth factors and volatilization temperatures measured for high-load particles clearly indicate that ternary nucleation is involved in particle formation.

The method outlined provides for emission factor measurements to be made for unmodified vehicles driving under real world conditions at minimal cost. The method consists of a plume capture trailer towed behind a test vehicle. The trailer collects a sample of the naturally diluted plume in a 200 L conductive bag and this is delivered immediately to a mobile laboratory for subsequent analysis of particulate and gaseous emissions. The method offers low test turnaround times with the potential to complete much larger numbers of emission factor measurements than have been possible using dynamometer testing. Samples can be collected at distances up to 3 m from the exhaust pipe allowing investigation of early dilution processes. Particle size distribution measurements, as well as particle number and mass emission factor measurements, based on naturally diluted plumes are presented. A dilution profile relating the plume dilution ratio to distance from the vehicle tail pipe for a diesel passenger vehicle is also presented. Such profiles are an essential input for new mechanistic roadway air quality models.

Particulate emissions from 11 gasoline powered and 2 liquefied petroleum (LPG) powered passenger vehicles were characterised during the Accelerated Simulation Mode driving cycles on a chassis dynamometer. The test fleet consisted of 10 catalyst-equipped vehicles operated with unleaded gasoline (5 Ford Falcons and 5 Holden Commodores), 2 LPG powered vehicles (both Ford Falcons), and 1 older type noncatalyst vehicle operated with leaded gasoline. Particulate characterisation included determination of total particulate number concentration and size distribution using the Scanning Mobility Particle Sizer (SMPS) and the Aerodynamic Particle Sizer (APS). The average particle number concentrations in the SMPS range for all modes was lower for Ford Falcons and somewhat higher for Commodores, with values of 1.5x104 and 4.1x104 cm-3, respectively. This difference is significant and was observed for all modes. The number concentration levels were higher for the LPG fuelled cars (8.4x104 cm-3) and for the leaded gasoline powered vehicle (7.9x105 cm-3). There was not a significant variation in particle count median diameter in the SMPS and the APS ranges, either for different operating conditions of the vehicles investigated, or between different vehicle groups. The observed size distributions were bimodal with average values of CMD ranged from 39.1 to 60.2nm in the SMPS range and from 0.9 to 1.4µm in the APS range. The results obtained from this study can be used as a first order estimation towards emission inventories for vehicle groups included in the investigations.