Nitrous acid measurements were carried out during the MEGAPOLI summer and winter field campaigns at SIRTA observatory in Paris surroundings. Highly variable HONO levels were observed during the ...campaigns, ranging from 10 ppt to 500 ppt in summer and from 10 ppt to 1.7 ppb in winter. Significant HONO mixing ratios have also been measured during daytime hours, comprised between some tenth of ppt and 200 ppt for the summer campaign and between few ppt and 1 ppb for the winter campaign. Ancillary measurements, such as NOx, O3, photolysis frequencies, meteorological parameters (pressure, temperature, relative humidity, wind speed and wind direction), black carbon concentration, total aerosol surface area, boundary layer height and soil moisture, were conducted during both campaigns. In addition, for the summer period, OH radical measurements were made with a CIMS (Chemical Ionisation Mass Spectrometer). This large dataset has been used to investigate the HONO budget in a suburban environment. To do so, calculations of HONO concentrations using PhotoStationary State (PSS) approach have been performed, for daytime hours. The comparison of these calculations with measured HONO concentrations revealed an underestimation of the calculations making evident a missing source term for both campaigns. This unknown HONO source exhibits a bell-shaped like average diurnal profile with a maximum around noon of approximately 0.7 ppb h−1 and 0.25 ppb h−1, during summer and winter respectively. This source is the main HONO source during daytime hours for both campaigns. In both cases, this source shows a slight positive correlation with J(NO2) and the product between J(NO2) and soil moisture. This original approach had, thus, indicated that this missing source is photolytic and might be heterogeneous occurring at ground surface and involving water content available on the ground.
Measurements of hydroxyl (OH) and hydroperoxy (HO2*) radical concentrations were made at the Pasadena ground site during the CalNex‐LA 2010 campaign using the laser‐induced fluorescence‐fluorescence ...assay by gas expansion technique. The measured concentrations of OH and HO2* exhibited a distinct weekend effect, with higher radical concentrations observed on the weekends corresponding to lower levels of nitrogen oxides (NOx). The radical measurements were compared to results from a zero‐dimensional model using the Regional Atmospheric Chemical Mechanism‐2 constrained by NOx and other measured trace gases. The chemical model overpredicted measured OH concentrations during the weekends by a factor of approximately 1.4 ± 0.3 (1σ), but the agreement was better during the weekdays (ratio of 1.0 ± 0.2). Model predicted HO2* concentrations underpredicted by a factor of 1.3 ± 0.2 on the weekends, while measured weekday concentrations were underpredicted by a factor of 3.0 ± 0.5. However, increasing the modeled OH reactivity to match the measured total OH reactivity improved the overall agreement for both OH and HO2* on all days. A radical budget analysis suggests that photolysis of carbonyls and formaldehyde together accounted for approximately 40% of radical initiation with photolysis of nitrous acid accounting for 30% at the measurement height and ozone photolysis contributing less than 20%. An analysis of the ozone production sensitivity reveals that during the week, ozone production was limited by volatile organic compounds throughout the day during the campaign but NOx limited during the afternoon on the weekends.
Key Points
Measurements of OH and HO2 during CalNex‐LA displayed a weekend effect
Modeled OH and HO2 agreed with measurements after accounting for missing OH reactivity
Ozone production was VOC limited on the weekdays but NOx limited on the weekends
Chemical Ionisation Mass Spectrometer measurements of hydroxyl radical (OH) and the sum of hydroperoxy and organic peroxy (HO2+RO2) radicals were conducted during the MEGAPOLI summer field campaign ...at the SIRTA observatory near Paris, France, in July 2009. OH and (HO2+RO2) showed a typical diurnal variation with averaged daytime maxima values around 5×106 and 1.2×108 molecule cm−3, respectively. Simultaneously, a large number of ancillary measurements, such as NOx, O3, HONO, HCHO and other VOCs were also conducted. These data provide an opportunity to assess our understanding of the radical chemistry in a suburban environment by comparing the radical observations to calculations. First, OH mixing ratios were estimated by a simple Photo Stationary State (PSS) calculation. PSS calculations overestimate the OH mixing ratio by 50%, especially at NOx mixing ratios lower than 10 ppb, suggesting that some loss processes were missing in the calculation at low NOx. Then, a photochemical box model simulation based on the Master Chemical Mechanism (MCM) and constrained by ancillary measurements was run to calculate radical concentrations. Three different modelling procedures were tested, varying the way the unconstrained secondary species were estimated, to cope with the unavoidable lack of their measurements. They led to significant differences in simulated radical concentrations. OH and (HO2+RO2) concentrations estimated by two selected model version were compared with measurements. These versions of the model were chosen because they lead, respectively, to the higher and lower simulated radical concentrations and are thus the two extremes versions. The box model showed better results than PSS calculations, with a slight overestimation of 12% and 5%, for OH and (HO2+RO2) respectively, in average for the reference model, and an overestimation of approximately 20% for OH and an underestimation for (HO2+RO2) for the other selected model version. Thus, we can conclude from our study that OH and (HO2+RO2) radical levels agree on average with observations within the uncertainty range. Finally, an analysis of the radical budget, on a daily basis (06:00–18:00 UTC), indicates that HONO photolysis (~35%), O3 photolysis (~23%), and aldehydes and ketones photolysis (~16% for formaldehyde and 18% for others) are the main radical initiation pathways. According to the MCM modelling, the reactions of RO2 with NO2 (~19%), leading mainly to PAN formation, is a significant termination pathway in addition to the main net loss via reaction of OH with NO2 (~50%).
During July 2009, a one-month measurement campaign was performed in the megacity of Paris. Amongst other measurement platforms, three stationary sites distributed over an area of 40 km in diameter in ...the greater Paris region enabled a detailed characterization of the aerosol particle and gas phase. Simulation results from the FLEXPART dispersion model were used to distinguish between different types of air masses sampled. It was found that the origin of air masses had a large influence on measured mass concentrations of the secondary species particulate sulphate, nitrate, ammonium, and oxygenated organic aerosol measured with the Aerodyne aerosol mass spectrometer in the submicron particle size range: particularly high concentrations of these species (about 4 mu g m super(-3), 2 mu g m super(-3), 2 mu g m super(-3), and 7 mu g m super(-3), respectively) were measured when aged material was advected from continental Europe, while for air masses originating from the Atlantic, much lower mass concentrations of these species were observed (about 1 mu g m super(-3), 0.2 mu g m super(-3), 0.4 mu g m super(-3), and 1-3 mu g m super(-3), respectively). For the primary emission tracers hydrocarbon-like organic aerosol, black carbon, and NO sub(x) it was found that apart from diurnal source strength variations and proximity to emission sources, local meteorology had the largest influence on measured concentrations, with higher wind speeds leading to larger dilution and therefore smaller measured concentrations. Also the shape of particle size distributions was affected by wind speed and air mass origin. Quasi-Lagrangian measurements performed under connected flow conditions between the three stationary sites were used to estimate the influence of the Paris emission plume onto its surroundings, which was found to be rather small. Rough estimates for the impact of the Paris emission plume on the suburban areas can be inferred from these measurements: Volume mixing ratios of 1-14 ppb of NO sub(x), and upper limits for mass concentrations of about 1.5 mu g m super(-3) of black carbon and of about 3 mu g m super(-3) of hydrocarbon-like organic aerosol can be deduced which originate from both, local emissions and the overall Paris emission plume. The secondary aerosol particle phase species were found to be not significantly influenced by the Paris megacity, indicating their regional origin. The submicron aerosol mass concentrations of particulate sulphate, nitrate, and ammonium measured during time periods when air masses were advected from eastern central Europe were found to be similar to what has been found from other measurement campaigns in Paris and south-central France for this type of air mass origin, indicating that the results presented here are also more generally valid.
Secondary pollutants such as ozone, secondary inorganic aerosol, and secondary organic aerosol formed in the plumes of megacities can affect regional air quality. In the framework of the FP7/EU ...MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) project, an intensive campaign was launched in the greater Paris region in July 2009. The major objective was to quantify different sources of organic aerosol (OA) within a megacity and in its plume. In this study, we use airborne measurements aboard the French ATR-42 aircraft to evaluate the regional chemistry-transport model CHIMERE within and downwind of the Paris region. Two mechanisms of secondary OA (SOA) formation are used, both including SOA formation from oxidation and chemical aging of primary semivolatile and intermediate volatility organic compounds (SI-SOA) in the volatility basis set (VBS) framework. As for SOA formed from traditional VOC (volatile organic compound) precursors (traditional SOA), one applies chemical aging in the VBS framework adopting different SOA yields for high- and low-NOx environments, while another applies a single-step oxidation scheme without chemical aging. Two emission inventories are used for discussion of emission uncertainties. The slopes of the airborne OA levels versus Ox (i.e., O3 + NO2) show SOA formation normalized with respect to photochemical activity and are used for specific evaluation of the OA scheme in the model. The simulated slopes were overestimated slightly by factors of 1.1, 1.7 and 1.3 with respect to those observed for the three airborne measurements, when the most realistic "high-NOx" yields for traditional SOA formation in the VBS scheme are used in the model. In addition, these slopes are relatively stable from one day to another, which suggests that they are characteristic for the given megacity plume environment. The configuration with increased primary organic aerosol (POA) emissions and with a single-step oxidation scheme of traditional SOA also agrees with the OA / Ox slopes (about ± 50 % with respect to the observed ones); however, it underestimates the background. Both configurations are coherent with observed OA plume buildup, but they show very different SI-SOA and traditional anthropogenic SOA (ASOA) contributions. It is hence concluded that available theoretical knowledge and available data in this study are not sufficient to discern the relative contributions of different types of anthropogenic SOA in the Paris pollution plume, while its sum is correctly simulated. Based on these simulations, for specific plumes, the anthropogenic OA buildup can reach between 8 and 10μg m−3. For the average of the month of July 2009, maximum OA increases due to emissions from the Paris agglomeration are noticed close to the agglomeration at various length scales: several tens (for primary OA) to hundreds (for SI-SOA and ASOA) of kilometers from the Paris agglomeration. In addition, BSOA (SOA formed from biogenic VOC precursors) is an important contributor to regional OA levels (inside and outside the Paris plume).
First- and higher order-generation products formed from the oxidation of isoprene and methacrolein with OH radicals in the presence of NOx have been studied in a simulation chamber. Significant ...oxidation rates have been maintained for up to 7 h, allowing the study of highly oxidized products. Gas-phase product distribution and yields were obtained, and show good agreement with previous studies. Secondary organic aerosol (SOA) formation has also been investigated. SOA mass yields from previous studies show large discrepancies. The mass yields obtained here were consistent with the lowest values found in the literature, and more specifically in agreement with studies carried out with natural light or artificial lamps with emission similar to the solar spectrum. Differences in light source are therefore proposed to explain partially the discrepancies observed between different studies in the literature for both isoprene- and methacrolein-SOA mass yields. There is a high degree of similarity between the SOA mass spectra from isoprene and methacrolein photooxidation, thus strengthening the importance of the role of methacrolein in SOA formation from isoprene photooxidation under our experimental conditions (i.e., presence of NOx and long term oxidation). According to our results, SOA mass yields from both isoprene and methacrolein in the atmosphere could be lower than suggested by most of the current chamber studies.
The MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) experiment took place in July 2009. The ...aim of this campaign was to study the aging and reactions of aerosol and gas-phase emissions in the city of Paris. Three ground-based measurement sites and several mobile platforms including instrument equipped vehicles and the ATR-42 aircraft were involved. We present here the variations in particle- and gas-phase species over the city of Paris, using a combination of high-time resolution measurements aboard the ATR-42 aircraft. Particle chemical composition was measured using a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS), giving detailed information on the non-refractory submicron aerosol species. The mass concentration of black carbon (BC), measured by a particle absorption soot photometer (PSAP), was used as a marker to identify the urban pollution plume boundaries. Aerosol mass concentrations and composition were affected by air-mass history, with air masses that spent longest time over land having highest fractions of organic aerosol and higher total mass concentrations. The Paris plume is mainly composed of organic aerosol (OA), BC, and nitrate aerosol, as well as high concentrations of anthropogenic gas-phase species such as toluene, benzene, and NOx. Using BC and CO as tracers for air-mass dilution, we observe the ratio of Delta OA / Delta BC and Delta OA / Delta CO increase with increasing photochemical age (-log(NOx / NOy)). Plotting the equivalent ratios of different organic aerosol species (LV-OOA, SV-OOA, and HOA) illustrate that the increase in OA is a result of secondary organic aerosol (SOA) formation. Within Paris the changes in the Delta OA / Delta CO are similar to those observed during other studies in London, Mexico City, and in New England, USA. Using the measured SOA volatile organic compounds (VOCs) species together with organic aerosol formation yields, we were able to predict ~50% of the measured organics. These airborne measurements during the MEGAPOLI experiment show that urban emissions contribute to the formation of OA and have an impact on aerosol composition on a regional scale.
The impact of cloud events on isoprene secondary organic aerosol (SOA) formation has been studied from an isoprene ∕ NOx ∕ light system in an atmospheric simulation chamber. It was shown that the ...presence of a liquid water cloud leads to a faster and higher SOA formation than under dry conditions. When a cloud is generated early in the photooxidation reaction, before any SOA formation has occurred, a fast SOA formation is observed with mass yields ranging from 0.002 to 0.004. These yields are 2 and 4 times higher than those observed under dry conditions. When the cloud is generated at a later photooxidation stage, after isoprene SOA is stabilized at its maximum mass concentration, a rapid increase (by a factor of 2 or higher) of the SOA mass concentration is observed. The SOA chemical composition is influenced by cloud generation: the additional SOA formed during cloud events is composed of both organics and nitrate containing species. This SOA formation can be linked to the dissolution of water soluble volatile organic compounds (VOCs) in the aqueous phase and to further aqueous phase reactions. Cloud-induced SOA formation is experimentally demonstrated in this study, thus highlighting the importance of aqueous multiphase systems in atmospheric SOA formation estimations.
The hydroxyl (OH) radical is an important oxidant in the troposphere, which controls the lifetime of most air quality- and climate-related trace gases. However, there are still uncertainties ...concerning its atmospheric budget, and integrated measurements of OH sinks have been valuable to improve this aspect. Among the analytical tools used for measuring total OH reactivity in ambient air, the comparative reactivity method (CRM) is spreading rapidly in the atmospheric community. However, measurement artifacts have been highlighted for this technique, and additional work is needed to fully characterize them. In this study, we present the new Mines Douai CRM instrument, with an emphasis on the corrections that need to be applied to ambient measurements of total OH reactivity. Measurement artifacts identified in the literature have been investigated, including (1) a correction for a change in relative humidity between the measurement steps leading to different OH levels, (2) the formation of spurious OH in the sampling reactor when hydroperoxy radicals (HO2) react with nitrogen monoxide (NO), (3) not operating the CRM under pseudo-first-order kinetics, and (4) the dilution of ambient air inside the reactor. The dependences of these artifacts on various measurable parameters, such as the pyrrole-to-OH ratio and the bimolecular reaction rate constants of ambient trace gases with OH, have also been studied. Based on these observations, parameterizations are proposed to correct ambient OH reactivity measurements. On average, corrections of 5.2 ± 3.2, 9.2 ± 15.7, and 8.5 ± 5.8 s−1 were respectively observed for (1), (2) and (3) during a field campaign performed in Dunkirk, France (summer 2014). Numerical simulations have been performed using a box model to check whether experimental observations mentioned above are consistent with our understanding of the chemistry occurring in the CRM reactor. Two different chemical mechanisms have been shown to reproduce the magnitude of corrections (2) and (3). In addition, these simulations reproduce their dependences on the pyrrole-to-OH ratio and on bimolecular reaction rate constants of gases reacting with OH. The good agreement found between laboratory experiments and model simulations gives us confidence in the proposed parameterizations. However, it is worth noting that the numerical values given in this study are suitable for the Mines Douai instrument and may not be appropriate for other CRM instruments. It is recommended that each group characterize its own instrument following the recommendations given in this study. An assessment of performances for the Mines Douai instrument, including a propagation of errors from the different corrections, indicates a limit of detection of 3.0 s−1 and total uncertainties of 17–25 % for OH reactivity values higher than 15 s−1 and NOx mixing ratios lower than 30 ppbv.
The hydroxyl radical (OH) plays a key role in the atmosphere, as it initiates most of the oxidation processes of volatile organic compounds (VOCs), and can ultimately lead to the formation of ozone ...and secondary organic aerosols (SOAs). There are still uncertainties associated with the OH budget assessed using current models of atmospheric chemistry and direct measurements of OH sources and sinks have proved to be valuable tools to improve our understanding of the OH chemistry. The total first order loss rate of OH, or total OH reactivity, can be directly measured using three different methods, such as the following: total OH loss rate measurement, laser-induced pump and probe technique and comparative reactivity method. Observations of total OH reactivity are usually coupled to individual measurements of reactive compounds in the gas phase, which are used to calculate the OH reactivity. Studies using the three methods have highlighted that a significant fraction of OH reactivity is often not explained by individually measured reactive compounds and could be associated to unmeasured or unknown chemical species. Therefore accurate and reproducible measurements of OH reactivity are required. The comparative reactivity method (CRM) has demonstrated to be an advantageous technique with an extensive range of applications, and for this reason it has been adopted by several research groups since its development. However, this method also requires careful corrections to derive ambient OH reactivity. Herein we present an intercomparison exercise of two CRM instruments, CRM-LSCE (Laboratoire des Sciences du Climat et de l'Environnement) and CRM-MD (Mines Douai), conducted during July 2013 at the Mediterranean site of Ersa, Cape Corsica, France. The intercomparison exercise included tests to assess the corrections needed by the two instruments to process the raw data sets as well as OH reactivity observations. The observation was divided in three parts: 2 days of plant emissions (8–9 July), 2 days of ambient measurements (10–11 July) and 2 days (12–13 July) of plant emissions. We discuss in detail the experimental approach adopted and how the data sets were processed for both instruments. Corrections required for the two instruments lead to higher values of reactivity in ambient air; overall 20 % increase for CRM-MD and 49 % for CRM-LSCE compared to the raw data. We show that ambient OH reactivity measured by the two instruments agrees very well (correlation described by a linear least squares fit with a slope of 1 and R2 of 0.75). This study highlights that ambient measurements of OH reactivity with differently configured CRM instruments yield consistent results in a low NOx (NO + NO2), terpene rich environment, despite differential corrections relevant to each instrument. Conducting more intercomparison exercises, involving more CRM instruments operated under different ambient and instrumental settings will help in assessing the variability induced due to instrument-specific corrections further.
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