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Ozone is a crucial air pollutant that damages human health and vegetation. As it is related to the photo-oxidation of the nitrogen oxides and volatile organic compounds, the summertime reduction of these precursors is the primary focus of current ozone mitigation strategies. During ozone pollution episodes in eastern China, an observed accumulation of daily total oxidants (Ox=NO2+O3) in cool seasons (spring and autumn: 60 ppb and winter 40 ppb) is comparable to that in summer (60 ppb), indicating fast photochemical production of secondary pollutants including ozone over the year. Unrecognized fast radical primary productions are found to counteract the increased termination of hydroxyl radical and unfavorable meteorological conditions to maintain the rapid total oxidant formations in cool seasons. Elucidating and regulating the primary radical sources may be critical for the secondary air pollution control in cool seasons.

The secondary organic aerosol (SOA) mass yields from NO3 oxidation of a series of biogenic volatile organic compounds (BVOCs), consisting of five monoterpenes and one sesquiterpene (α-pinene, β-pinene, Δ-3-carene, limonene, sabinene, and β-caryophyllene), were investigated in a series of continuous flow experiments in a 10 m(3) indoor Teflon chamber. By making in situ measurements of the nitrate radical and employing a kinetics box model, we generate time-dependent yield curves as a function of reacted BVOC. SOA yields varied dramatically among the different BVOCs, from zero for α-pinene to 38-65% for Δ-3-carene and 86% for β-caryophyllene at mass loading of 10 μg m(-3), suggesting that model mechanisms that treat all NO3 + monoterpene reactions equally will lead to errors in predicted SOA depending on each location's mix of BVOC emissions. In most cases, organonitrate is a dominant component of the aerosol produced, but in the case of α-pinene, little organonitrate and no aerosol is formed.

During the CalNex (California Research at the Nexus of Air Quality and Climate Change) field study in May-June 2010, measurements of volatile organic compounds (VOCs) were performed in the Los Angeles (LA) basin onboard a NOAA research aircraft and at a ground site located in Pasadena. A weekday-weekend effect in ozone, caused by lower NOx emissions due to reduced diesel truck traffic in the weekends, has been previously observed in Los Angeles and other cities. Measurements in the Caldecott tunnel show that emission ratios of VOCs do not vary with the day of the week, but measurements during CalNex2010 show a VOC weekday-weekend effect through faster photochemical processing at lower ambient NOx mixing ratios. Ambient VOC enhancement ratios of long-lived species such as benzene are the same between weekdays and weekends, whereas enhancement ratios of short-lived species, such as trimethyl benzene, are up to a factor of three lower on weekends. Based upon the observed differences in VOC enhancement ratios to CO, we determine that photochemical processing was on average 65%-75% faster on weekends during CalNex2010, which indicates that ambient OH radical concentrations were larger by this factor causing the observed change in VOC composition. A box model calculation based on the Master Chemical Mechanism was used to verify the increase in photochemical processing in the weekends. Key PointsSpatial and temporal photochemical processing in Los AngelesVOC weekday-weekend effectFaster photochemistry in weekends ©2013. American Geophysical Union. All Rights Reserved.

Organonitrates are important species in the atmosphere due to their impacts on NOx, HOx, and O3 budgets, and their potential to contribute to secondary organic aerosol (SOA) mass. This work presents a steady-state modelling approach to assess the impacts of changes in NOx and O3 concentrations on the organonitrates produced from isoprene oxidation. The diverse formation pathways to isoprene organonitrates dictate the responses of different groups of organonitrates to changes in O3 and NOx. For example, organonitrates predominantly formed from the OH-initiated oxidation of isoprene favour formation under lower ozone and moderate NOx concentrations, whereas organonitrates formed via day-time NO3 oxidation show the highest formation under high O3 concentrations with little dependence on NOx concentrations. Investigating the response of total organonitrates reveals complex and non-linear behaviour with implications that could inform expectations of changes to organonitrate concentrations as efforts are made to reduce NOx and O3 concentrations, including a region of NOx-O3 space where total organonitrate concentration is relatively insensitive to changes in NOx and O3. These conclusions are further contextualised by estimating the volatility of the isoprene organonitrates revealing the potential for high concentrations of low volatility species under high ozone conditions. [ABSTRACT FROM AUTHOR]

The gas-phase reaction of isoprene with the nitrate radical (NO3) was investigated in experiments in the outdoor SAPHIR chamber at atmospherically relevant conditions specifically with respect to the chemical lifetime and fate of nitrato-organic peroxy radicals (RO2). Observations of organic products were compared to concentrations expected from different chemical mechanisms: (1) The Master Chemical Mechanism, which simplifies the NO3 isoprene chemistry by only considering one RO2 conformer. (2) The chemical mechanism derived from experiments in the CalTech chamber, which considers different RO2 conformers. (3) The FZJ-NO3 isoprene mechanism derived from quantum chemical calculations, which in addition to the CalTech mechanism includes equilibrium reactions of RO2 conformers, unimolecular reactions of nitrate RO2 radicals and epoxidation reactions of nitrate alkoxy radicals. Measurements using mass spectrometer instruments give evidence that the new reactions pathways predicted by quantum chemical calculations play a role in the NO3 oxidation of isoprene. Hydroperoxy aldehydes (HPALD), which are specific for unimolecular reactions of nitrate RO2, were detected even in the presence of an OH scavenger excluding the possibility that concurrent oxidation by hydroxyl radicals (OH) is responsible for their formation. In addition, epoxy compounds, which are specific for the epoxidation reaction of nitrate alkoxy radicals, were detected. Measurements of methyl vinyl ketone (MVK) and methacrolein (MACR) concentrations confirm that the decomposition of nitrate alkoxy radicals implemented in the CalTech mechanism cannot compete with the ring-closure reactions predicted by quantumchemical calculations. The validity of the FZJ-NO3 isoprene mechanism is further supported by an accurate simulation of the measured hydroxyl radical (OH) reactivity. Nevertheless, the FZJ-NO3 isoprene mechanism needs further investigations with respect to the absolute importance of unimolecular reactions of nitrate RO2 and epoxidation reactions of nitrate alkoxy radicals. Absolute concentrations of specific organic nitrates such as nitrate hydroperoxides would be required to experimentally determine product yields and branching ratios of reactions but could not be measured in the chamber experiments due to the lack of calibration standards for these compounds. The temporal evolution of mass traces attributed to products species such as nitrate hydroperoxides, nitrate carbonyl, nitrate alcohols as well as hydroperoxy aldehydes observed by the mass spectrometer instruments demonstrates that further oxidation by the nitrate radical and ozone at atmospheric concentrations is not relevant on the typical time scale of one night (12 hours). However, oxidation by hydroxyl radicals present at night and potentially also produced from the decomposition of nitrate alkoxy radicals can contribute to their nocturnal chemical loss. [ABSTRACT FROM AUTHOR]

Total gaseous chlorine (TClg) measurements can improve our understanding of unknown sources of Cl to the atmosphere. Existing techniques for measuring TClg have been limited to offline analysis of extracted filters and do not provide suitable temporal information on fast atmospheric process. We describe high time-resolution in-situ measurements of TClg by combusting ambient air over a heated platinum (Pt) substrate coupled to a cavity ring-down spectrometer (CRDS). The method relies on the complete decomposition of TClg to release Cl atoms that react to form HCl, for which detection by CRDS has been shown to be fast and reliable. The method was validated using custom organochlorine permeation devices (PDs) that generated gas-phase dichloromethane (DCM), 1-chlorobutane (CB), and 1,3-dichloropropene (DCP). The optimal conversion temperature and residence time through the high-temperature furnace was 825 °C and 1.5 seconds, respectively. Complete conversion was indicated by the near unity orthogonal distance regression analysis slope (±σ) of 0.996 ± 0.012, 1.048 ± 0.006, and 1.027 ± 0.061 for DCM, CB, and DCP, respectively. Breaking these strong C-Cl bonds represents a proof of concept for complete conversion of all similar or weaker bonds that characterize all other TClg. We applied this technique to both outdoor and indoor environments and found reasonable comparisons in ambient background mixing ratios with the sum of expected HCl from known Cl species. We measured the converted TClg in an indoor environment during cleaning activities and observed varying levels of TClg comparable to previous studies. The method validated here is capable of measuring in-situ TClg and has a broad range of applications to make routine TClg measurements in a variety of applications. [ABSTRACT FROM AUTHOR]

Author(s): Peter M. Edwards [1, 2, 8]; Steven S. Brown (corresponding author) [1]; James M. Roberts [1]; Ravan Ahmadov [1, 2]; Robert M. Banta [1]; Joost A. deGouw [1, 2]; [...]

Low cost sensors (LCS) are an appealing solution to the problem of spatial resolution in air quality measurement, but they currently do not have the same analytical performance as regulatory reference methods. Individual sensors can be susceptible to analytical cross interferences, have random signal variability and experience drift over short, medium and long timescales. To overcome some of the performance limitations of individual sensors we use a clustering approach using the instantaneous median signal from six identical electrochemical sensors to minimise the randomised drifts and inter-sensor differences. We report here a low power analytical device (< 200 W) that comprises of clusters of sensors for NO2, OX, CO and total VOC, and that measures supporting parameters such as water vapour and temperature. This was tested in the field against reference monitors, collecting ambient air pollution data in Beijing, China. Comparisons were made of NO2 and OX clustered sensor data against reference methods for calibrations derived from factory settings, in-field simple linear regression (SLR) and then against three machine learning (ML) algorithms. The parametric supervised ML algorithms boosted regression trees (BRT) and boosted linear regression (BLR) and the non-parametric technique Gaussian Process (GP) used all available sensor data to improve the measurement estimate of NO2 and OX. In all cases ML produced an observational value that was closer to reference measurements than SLR alone. In combination, sensor clustering and ML generated sensor data of a quality that was close to that of regulatory measurements (using the RSME metric) yet retained a very substantial cost and power advantage. [ABSTRACT FROM AUTHOR]

Nighttime reaction of nitrate radicals (NO3) with biogenic volatile organic compounds (BVOC) has been proposed as a potentially important but also highly uncertain source of secondary organic aerosol (SOA). The southeastern United States has both high BVOC and nitrogen oxide (NOx) emissions, resulting in a large model-predicted NO3-BVOC source of SOA. Coal-fired power plants in this region constitute substantial NOx emissions point sources into a nighttime atmosphere characterized by high regionally widespread concentrations of isoprene. In this paper, we exploit nighttime aircraft observations of these power plant plumes, in which NO3 radicals rapidly remove isoprene, to obtain field-based estimates of the secondary organic aerosol yield from NO3 Cisoprene. Observed in-plume increases in nitrate aerosol are consistent with organic nitrate aerosol production from NO3 Cisoprene, and these are used to determine molar SOA yields, for which the average over nine plumes is 9% (±5%). Corresponding mass yields depend on the assumed molecular formula for isoprene-NO3-SOA, but the average over nine plumes is 27% (±14%), on average larger than those previously measured in chamber studies (12%-14% mass yield as 1OA=1VOC after oxidation of both double bonds). Yields are larger for longer plume ages. This suggests that ambient aging processes lead more effectively to condensable material than typical chamber conditions allow. We discuss potential mechanistic explanations for this difference, including longer ambient peroxy radical lifetimes and heterogeneous reactions of NO3-isoprene gas phase products. More in-depth studies are needed to better understand the aerosol yield and oxidation mechanism of NO3 radicalCisoprene, a coupled anthropogenic-biogenic source of SOA that may be regionally significant. [ABSTRACT FROM AUTHOR]