Secondary organic aerosol formation from in-use motor vehicle emissions using a potential aerosol mass reactor.

Secondary organic aerosol (SOA) formation from in-use vehicle emissions was investigated using a potential aerosol mass (PAM) flow reactor deployed in a highway tunnel in Pittsburgh, Pennsylvania. Experiments consisted of passing exhaust-dominated tunnel air through a PAM reactor over integrated hydroxyl radical (OH) exposures ranging from ∼ 0.3 to 9.3 days of equivalent atmospheric oxidation. Experiments were performed during heavy traffic periods when the fleet was at least 80% light-duty gasoline vehicles on a fuel-consumption basis. The peak SOA production occurred after 2-3 days of equivalent atmospheric oxidation. Additional OH exposure decreased the SOA production presumably due to a shift from functionalization to fragmentation dominated reaction mechanisms. Photo-oxidation also produced substantial ammonium nitrate, often exceeding the mass of SOA. Analysis with an SOA model highlight that unspeciated organics (i.e., unresolved complex mixture) are a very important class of precursors and that multigenerational processing of both gases and particles is important at longer time scales. The chemical evolution of the organic aerosol inside the PAM reactor appears to be similar to that observed in the atmosphere. The mass spectrum of the unoxidized primary organic aerosol closely resembles ambient hydrocarbon-like organic aerosol (HOA). After aging the exhaust equivalent to a few hours of atmospheric oxidation, the organic aerosol most closely resembles semivolatile oxygenated organic aerosol (SV-OOA) and then low-volatility organic aerosol (LV-OOA) at higher OH exposures. Scaling the data suggests that mobile sources contribute ∼ 2.9 ± 1.6 Tg SOA yr(-1) in the United States, which is a factor of 6 greater than all mobile source particulate matter emissions reported by the National Emissions Inventory. This highlights the important contribution of SOA formation from vehicle exhaust to ambient particulate matter concentrations in urban areas

Characterisation of La0.6Sr0.4Co0.2Fe0.8O3-\u3b4- Ba0.5Sr0.5Co0.8Fe0.2O3-\u3b4composite as cathode for solid oxide fuel cells

Mixture of La0.6Sr0.4Co0.2Fe0.8O3-\u3b4 and Ba0.5Sr0.5Co0.8Fe0.2O3-\u3b4, was investigated as promising cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs). The two perovskites possess high catalytic activity for the oxygen reduction (ORR), although some problems related to their chemical and structural stability have still to be overcome in view of improving durability of the cell performance. The achievement of a stable and high-performing composite material is the aim of this study. In principle, chemical equilibrium at the LSCF-BSCF interface may be reached through ions interdiffusion during the sintering process, resulting in the chemical stabilization of the material. The composite-cathode deposited on Ce0.8Sm0.2O2-\u3b4 electrolyte was then investigated by Electrochemical Impedance Spectroscopy (EIS) as a function of temperature, overpotential and time. The results exhibited an interesting electrochemical behavior of the electrode toward oxygen reduction reaction. XRD analysis was performed to detect structural modification during thermal or operation stages and it was found that after the sintering the two starting perovskites were no longer present; a new phase with a rhombohedral La0,4Sr0,6FeO3-type structure (LSF) is formed. An improvement in composite cathode durability has been detected under the considered operating conditions (200 mAcm-2, 700 \ub0C) in comparison with the pure BSCF electrode. The results confirmed this new electrode as promising system for further investigation as IT-SOFC cathode

Wave- and tidally-driven flow and sediment flux across a fringing coral reef : southern Molokai, Hawaii

This paper is not subject to U.S. copyright. The definitive version was published in Continental Shelf Research 24 (2004): 1397-1419, doi:10.1016/j.csr.2004.02.010.The fringing coral reef off the south coast of Molokai, Hawaii is currently being studied as part of a US Geological Survey (USGS) multi-disciplinary project that focuses on geologic and oceanographic processes that affect coral reef systems. For this investigation, four instrument packages were deployed across the fringing coral reef during the summer of 2001 to understand the processes governing fine-grained terrestrial sediment suspension on the shallow reef flat (h=1 m) and its advection across the reef crest and onto the deeper fore reef. The time–series measurements suggest the following conceptual model of water and fine-grained sediment transport across the reef: Relatively cool, clear water flows up onto the reef flat during flooding tides. At high tide, more deep-water wave energy is able to propagate onto the reef flat and larger Trade wind-driven waves can develop on the reef flat, thereby increasing sediment suspension. Trade wind-driven surface currents and wave breaking at the reef crest cause setup of water on the reef flat, further increasing the water depth and enhancing the development of depth-limited waves and sediment suspension. As the tide ebbs, the water and associated suspended sediment on the reef flat drains off the reef flat and is advected offshore and to the west by Trade wind- and tidally- driven currents. Observations on the fore reef show relatively high turbidity throughout the water column during the ebb tide. It therefore appears that high suspended sediment concentrations on the deeper fore reef, where active coral growth is at a maximum, are dynamically linked to processes on the muddy, shallow reef flat

Production of Secondary Organic Aerosol During Aging of Biomass Burning Smoke From Fresh Fuels and Its Relationship to VOC Precursors

After smoke from burning biomass is emitted into the atmosphere, chemical and physical processes change the composition and amount of organic aerosol present in the aged, diluted plume. During the fourth Fire Lab at Missoula Experiment, we performed smog-chamber experiments to investigate formation of secondary organic aerosol (SOA) and multiphase oxidation of primary organic aerosol (POA). We simulated atmospheric aging of diluted smoke from a variety of biomass fuels while measuring particle composition using high-resolution aerosol mass spectrometry. We quantified SOA formation using a tracer ion for low-volatility POA as a reference standard (akin to a naturally occurring internal standard). These smoke aging experiments revealed variable organic aerosol (OA) enhancements, even for smoke from similar fuels and aging mechanisms. This variable OA enhancement correlated well with measured differences in the amounts of emitted volatile organic compounds (VOCs) that could subsequently be oxidized to form SOA. For some aging experiments, we were able to predict the SOA production to within a factor of 2 using a fuel-specific VOC emission inventory that was scaled by burn-specific toluene measurements. For fires of coniferous fuels that were dominated by needle burning, volatile biogenic compounds were the dominant precursor class. For wiregrass fires, furans were the dominant SOA precursors. We used a POA tracer ion to calculate the amount of mass lost due to gas-phase oxidation and subsequent volatilization of semivolatile POA. Less than 5% of the POA mass was lost via multiphase oxidation-driven evaporation during up to 2 hr of equivalent atmospheric oxidation

A Comprehensive Approach to Improve Performance and Stability of State-of-the- Art Air Electrodes for Intermediate Temperature Reversible Cells: An Impedance Spectroscopy Analysis

Solid oxide fuel cells (SOFC) are devices for the transformation of chemical energy in electrical energy. SOFC appear very promising for their very high efficiency, in addition to the capability to work in reverse mode, which makes them suitable for integration in production units powered with renewables. Research efforts are currently addressed to find chemically and structurally stable materials, in order to improve performance stability during long-term operation. In this work, we examine different approaches for improving stability of two state-of-the-art perovskite materials, La0.6Sr0.4Co0.2Fe0.8O3-\uf064 (LSCF) and Ba0.5Sr0.5Co0.8Fe0.2O3-\uf064 (BSCF), very promising as air electrodes. Two different systems are considered: (i) LSCF and BSCF porous electrodes impregnated by a nano-sized La0.8Sr0.2MnO3-\uf064 layer and (ii) LSCF-BSCF composites with the two phases in different volume proportions. The study considers the results obtained by electrochemical impedance spectroscopy investigation, observing the polarisation resistance (Rp) of each system to evaluate performance in typical SOFC operating conditions. Furthermore, the behaviour of polarisation resistance under the effect of a net current load (cathodic) circulating for hundreds of hours is examined, as parameter to evaluate long-term performance stability

Ozonolysis of α-pinene: parameterization of secondary organic aerosol mass fraction

Existing parameterizations tend to underpredict the α-pinene aerosol mass fraction (AMF) or yield by a factor of 2–5 at low organic aerosol concentrations (<5 µg m<sup>−3</sup>). A wide range of smog chamber results obtained at various conditions (low/high NO<sub>x</sub>, presence/absence of UV radiation, dry/humid conditions, and temperatures ranging from 15–40°C) collected by various research teams during the last decade are used to derive new parameterizations of the SOA formation from α-pinene ozonolysis. Parameterizations are developed by fitting experimental data to a basis set of saturation concentrations (from 10<sup>−2</sup> to 10<sup>4</sup> µg m<sup>−3</sup>) using an absorptive equilibrium partitioning model. Separate parameterizations for α-pinene SOA mass fractions are developed for: 1) Low NO<sub>x</sub>, dark, and dry conditions, 2) Low NO<sub>x</sub>, UV, and dry conditions, 3) Low NO<sub>x</sub>, dark, and high RH conditions, 4) High NO<sub>x</sub>, dark, and dry conditions, 5) High NO<sub>x</sub>, UV, and dry conditions. According to the proposed parameterizations the α-pinene SOA mass fractions in an atmosphere with 5 µg m<sup>−3</sup> of organic aerosol range from 0.032 to 0.1 for reacted α-pinene concentrations in the 1 ppt to 5 ppb range

Reactive intermediates revealed in secondary organic aerosol formation from isoprene

Isoprene is a significant source of atmospheric organic aerosol; however, the oxidation pathways that lead to secondary organic aerosol (SOA) have remained elusive. Here, we identify the role of two key reactive intermediates, epoxydiols of isoprene (IEPOX = β-IEPOX + δ-IEPOX) and methacryloylperoxynitrate (MPAN), which are formed during isoprene oxidation under low- and high-NO_x conditions, respectively. Isoprene low-NO_x SOA is enhanced in the presence of acidified sulfate seed aerosol (mass yield 28.6%) over that in the presence of neutral aerosol (mass yield 1.3%). Increased uptake of IEPOX by acid-catalyzed particle-phase reactions is shown to explain this enhancement. Under high-NO_x conditions, isoprene SOA formation occurs through oxidation of its second-generation product, MPAN. The similarity of the composition of SOA formed from the photooxidation of MPAN to that formed from isoprene and methacrolein demonstrates the role of MPAN in the formation of isoprene high-NO_x SOA. Reactions of IEPOX and MPAN in the presence of anthropogenic pollutants (i.e., acidic aerosol produced from the oxidation of SO_2 and NO_2, respectively) could be a substantial source of “missing urban SOA” not included in current atmospheric models

High-spatial-resolution mapping and source apportionment of aerosol composition in Oakland, California, using mobile aerosol mass spectrometry

We investigated spatial and temporal patterns in the concentration and composition of submicron particulate matter (PM1) in Oakland, California, in the summer of 2017 using an aerosol mass spectrometer mounted in a mobile laboratory. We performed  ∼ 160&thinsp;h of mobile sampling in the city over a 20-day period. Measurements are compared for three adjacent neighborhoods with distinct land uses: a central business district (downtown), a residential district (West Oakland), and a major shipping port (port). The average organic aerosol (OA) concentration is 5.3&thinsp;µg&thinsp;m−3 and contributes  ∼ 50&thinsp;% of the PM1 mass. OA concentrations in downtown are, on average, 1.5&thinsp;µg&thinsp;m−3 higher than in West Oakland and port. We decomposed OA into three factors using positive matrix factorization: hydrocarbon-like OA (HOA; 20&thinsp;% average contribution), cooking OA (COA; 25&thinsp;%), and less-oxidized oxygenated OA (LO-OOA; 55&thinsp;%). The collective 45&thinsp;% contribution from primary OA (HOA&thinsp;+&thinsp;COA) emphasizes the importance of primary emissions in Oakland. The dominant source of primary OA shifts from HOA-rich in the morning to COA-rich after lunchtime. COA in downtown is consistently higher than West Oakland and port due to a large number of restaurants. HOA exhibits variability in space and time. The morning-time HOA concentration in downtown is twice that in port, but port HOA increases more than two-fold during midday, likely because trucking activity at the port peaks at that time. While it is challenging to mathematically apportion traffic-emitted OA between drayage trucks and cars, combining measurements of OA with black carbon and CO suggests that while trucks have an important effect on OA and BC at the port, gasoline-engine cars are the dominant source of traffic emissions in the rest of Oakland. Despite the expectation of being spatially uniform, LO-OOA also exhibits spatial differences. Morning-time LO-OOA in downtown is roughly 25&thinsp;% ( ∼ 0.6&thinsp;µg&thinsp;m−3) higher than the rest of Oakland. Even as the entire domain approaches a more uniform photochemical state in the afternoon, downtown LO-OOA remains statistically higher than West Oakland and port, suggesting that downtown is a microenvironment with higher photochemical activity. Higher concentrations of particulate sulfate (also of secondary origin) with no direct sources in Oakland further reflect higher photochemical activity in downtown. A combination of several factors (poor ventilation of air masses in street canyons, higher concentrations of precursor gases, higher concentrations of the hydroxyl radical) likely results in the proposed high photochemical activity in downtown. Lastly, through Van Krevelen analysis of the elemental ratios (H&thinsp;∕&thinsp;C, O&thinsp;∕&thinsp;C) of the OA, we show that OA in Oakland is more chemically reduced than several other urban areas. This underscores the importance of primary emissions in Oakland. We also show that mixing of oceanic air masses with these primary emissions in Oakland is an important processing mechanism that governs the overall OA composition in Oakland.</p

Development of a general calibration model and long-term performance evaluation of low-cost sensors for air pollutant gas monitoring

Assessing the intracity spatial distribution and temporal variability in air quality can be facilitated by a dense network of monitoring stations. However, the cost of implementing such a network can be prohibitive if traditional high-quality, expensive monitoring systems are used. To this end, the Real-time Affordable Multi-Pollutant (RAMP) monitor has been developed, which can measure up to five gases including the criteria pollutant gases carbon monoxide (CO), nitrogen dioxide (NO2), and ozone (O3), along with temperature and relative humidity. This study compares various algorithms to calibrate the RAMP measurements including linear and quadratic regression, clustering, neural networks, Gaussian processes, and hybrid random forest–linear regression models. Using data collected by almost 70 RAMP monitors over periods ranging up to 18 months, we recommend the use of limited quadratic regression calibration models for CO, neural network models for NO, and hybrid models for NO2 and O3 for any low-cost monitor using electrochemical sensors similar to those of the RAMP. Furthermore, generalized calibration models may be used instead of individual models with only a small reduction in overall performance. Generalized models also transfer better when the RAMP is deployed to other locations. For long-term deployments, it is recommended that model performance be re-evaluated and new models developed periodically, due to the noticeable change in performance over periods of a year or more. This makes generalized calibration models even more useful since only a subset of deployed monitors are needed to build these new models. These results will help guide future efforts in the calibration and use of low-cost sensor systems worldwide.</p

Production of Secondary Organic Aerosol During Aging of Biomass Burning Smoke From Fresh Fuels and Its Relationship to VOC Precursors

After smoke from burning biomass is emitted into the atmosphere, chemical and physical processes change the composition and amount of organic aerosol present in the aged, diluted plume. During the fourth Fire Lab at Missoula Experiment, we performed smog-chamber experiments to investigate formation of secondary organic aerosol (SOA) and multiphase oxidation of primary organic aerosol (POA). We simulated atmospheric aging of diluted smoke from a variety of biomass fuels while measuring particle composition using high-resolution aerosol mass spectrometry. We quantified SOA formation using a tracer ion for low-volatility POA as a reference standard (akin to a naturally occurring internal standard). These smoke aging experiments revealed variable organic aerosol (OA) enhancements, even for smoke from similar fuels and aging mechanisms. This variable OA enhancement correlated well with measured differences in the amounts of emitted volatile organic compounds (VOCs) that could subsequently be oxidized to form SOA. For some aging experiments, we were able to predict the SOA production to within a factor of 2 using a fuel-specific VOC emission inventory that was scaled by burn-specific toluene measurements. For fires of coniferous fuels that were dominated by needle burning, volatile biogenic compounds were the dominant precursor class. For wiregrass fires, furans were the dominant SOA precursors. We used a POA tracer ion to calculate the amount of mass lost due to gas-phase oxidation and subsequent volatilization of semivolatile POA. Less than 5% of the POA mass was lost via multiphase oxidation-driven evaporation during up to 2 hr of equivalent atmospheric oxidation