ALBERT

Description: Formaldehyde (HCHO) has been measured from space for more than 2 decades. Owing to its short atmospheric lifetime, satellite HCHO data are used widely as a proxy of volatile organic compounds (VOCs; please refer to Appendix A for abbreviations and acronyms), providing constraints on underlying emissions and chemistry. However, satellite HCHO products from different satellite sensors using different algorithms have received little validation so far. The accuracy and consistency of HCHO retrievals remain largely unclear. Here we develop a validation platform for satellite HCHO retrievals using in situ observations from 12 aircraft campaigns with a chemical transport model (GEOS-Chem) as the intercomparison method. Application to the NASA operational OMI HCHO product indicates negative biases (−44.5 % to −21.7 %) under high-HCHO conditions, while it indicates high biases (+66.1 % to +112.1 %) under low-HCHO conditions. Under both conditions, HCHO a priori vertical profiles are likely not the main driver of the biases. By providing quick assessment of systematic biases in satellite products over large domains, the platform facilitates, in an iterative process, optimization of retrieval settings and the minimization of retrieval biases. It is also complementary to localized validation efforts based on ground observations and aircraft spirals.

Description: Aromatic hydrocarbons make up a large fraction of anthropogenic volatile organic compounds and contribute significantly to the production of tropospheric ozone and secondary organic aerosol (SOA). Four toluene and four 1,2,4-trimethylbenzene (1,2,4-TMB) photooxidation experiments were performed in an environmental chamber under relevant polluted conditions (NOx∼10 ppb). An extensive suite of instrumentation including two proton-transfer-reaction mass spectrometers (PTR-MS) and two chemical ionisation mass spectrometers (NH4+ CIMS and I− CIMS) allowed for quantification of reactive carbon in multiple generations of hydroxyl radical (OH)-initiated oxidation. Oxidation of both species produces ring-retaining products such as cresols, benzaldehydes, and bicyclic intermediate compounds, as well as ring-scission products such as epoxides and dicarbonyls. We show that the oxidation of bicyclic intermediate products leads to the formation of compounds with high oxygen content (an O:C ratio of up to 1.1). These compounds, previously identified as highly oxygenated molecules (HOMs), are produced by more than one pathway with differing numbers of reaction steps with OH, including both auto-oxidation and phenolic pathways. We report the elemental composition of these compounds formed under relevant urban high-NO conditions. We show that ring-retaining products for these two precursors are more diverse and abundant than predicted by current mechanisms. We present the speciated elemental composition of SOA for both precursors and confirm that highly oxygenated products make up a significant fraction of SOA. Ring-scission products are also detected in both the gas and particle phases, and their yields and speciation generally agree with the kinetic model prediction.

Description: Sources and sinks of isoprene oxidation products from low-NOx isoprene chemistry have been studied at the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber with a custom-built selective reagent ion time-of-flight mass spectrometer (SRI-ToF-MS), which allows quantitative measurement of isoprene hydroxy hydroperoxides (ISOPOOHs). The measured concentrations of the main oxidation products were compared to chemical box model simulations based on the Leeds Master Chemical Mechanism (MCM) v3.3. The modeled ISOPOOH concentrations are a factor of 20 higher than the observed concentrations, and methyl vinyl ketone (MVK) and methacrolein (MACR) concentrations are up to a factor of 2 lower compared to observations, despite the artifact-free detection method. Addition of catalytic conversion of 1,2-ISOPOOH and 4,3-ISOPOOH to methyl vinyl ketone (MVK) and methacrolein (MACR) on the stainless-steel surface of the chamber to the chemical mechanism resolves the discrepancy between model predictions and observation. This suggests that isoprene chemistry in a metal chamber under low-NOx conditions cannot be described by a pure gas phase model alone. Biases in the measurement of ISOPOOH, MVK, and MACR can be caused not only intra-instrumentally but also by the general experimental setup. The work described here extends the role of heterogeneous reactions affecting gas phase composition and properties from instrumental surfaces, described previously, to general experimental setups. The role of such conversion reactions on real environmental surfaces is yet to be explored.

Description: The photooxidation of methyl vinyl ketone (MVK) was investigated in the atmospheric simulation chamber SAPHIR for conditions at which organic peroxy radicals (RO2) mainly reacted with NO (“high NO” case) and for conditions at which other reaction channels could compete (“low NO” case). Measurements of trace gas concentrations were compared to calculated concentration time series applying the Master Chemical Mechanism (MCM version 3.3.1). Product yields of methylglyoxal and glycolaldehyde were determined from measurements. For the high NO case, the methylglyoxal yield was (19 ± 3) % and the glycolaldehyde yield was (65 ± 14) %, consistent with recent literature studies. For the low NO case, the methylglyoxal yield reduced to (5 ± 2) % because other RO2 reaction channels that do not form methylglyoxal became important. Consistent with literature data, the glycolaldehyde yield of (37 ± 9) % determined in the experiment was not reduced as much as implemented in the MCM, suggesting additional reaction channels producing glycolaldehyde. At the same time, direct quantification of OH radicals in the experiments shows the need for an enhanced OH radical production at low NO conditions similar to previous studies investigating the oxidation of the parent VOC isoprene and methacrolein, the second major oxidation product of isoprene. For MVK the model–measurement discrepancy was up to a factor of 2. Product yields and OH observations were consistent with assumptions of additional RO2 plus HO2 reaction channels as proposed in literature for the major RO2 species formed from the reaction of MVK with OH. However, this study shows that also HO2 radical concentrations are underestimated by the model, suggesting that additional OH is not directly produced from RO2 radical reactions, but indirectly via increased HO2. Quantum chemical calculations show that HO2 could be produced from a fast 1,4-H shift of the second most important MVK derived RO2 species (reaction rate constant 0.003 s−1). However, additional HO2 from this reaction was not sufficiently large to bring modelled HO2 radical concentrations into agreement with measurements due to the small yield of this RO2 species. An additional reaction channel of the major RO2 species with a reaction rate constant of (0.006 ± 0.004) s−1 would be required that produces concurrently HO2 radicals and glycolaldehyde to achieve model–measurement agreement. A unimolecular reaction similar to the 1,5-H shift reaction that was proposed in literature for RO2 radicals from MVK would not explain product yields for conditions of experiments in this study. A set of H-migration reactions for the main RO2 radicals were investigated by quantum chemical and theoretical kinetic methodologies, but did not reveal a contributing route to HO2 radicals or glycolaldehyde.

Description: Chemical ionization mass spectrometry (CIMS) instruments routinely detect hundreds of oxidized organic compounds in the atmosphere. A major limitation of these instruments is the uncertainty in their sensitivity to many of the detected ions. We describe the development of a new high-resolution time-of-flight chemical ionization mass spectrometer that operates in one of two ionization modes: using either ammonium ion ligand-switching reactions such as for NH4+ CIMS or proton transfer reactions such as for proton-transfer-reaction mass spectrometer (PTR-MS). Switching between the modes can be done within 2 min. The NH4+ CIMS mode of the new instrument has sensitivities of up to 67 000 dcps ppbv−1 (duty-cycle-corrected ion counts per second per part per billion by volume) and detection limits between 1 and 60 pptv at 2σ for a 1 s integration time for numerous oxygenated volatile organic compounds. We present a mass spectrometric voltage scanning procedure based on collision-induced dissociation that allows us to determine the stability of ammonium-organic ions detected by the NH4+ CIMS instrument. Using this procedure, we can effectively constrain the sensitivity of the ammonia chemical ionization mass spectrometer to a wide range of detected oxidized volatile organic compounds for which no calibration standards exist. We demonstrate the application of this procedure by quantifying the composition of secondary organic aerosols in a series of laboratory experiments.

Description: Organic nitrate chemistry is the primary control over the lifetime of nitrogen oxides (NOx) in rural and remote continental locations. As NOx emissions decrease, organic nitrate chemistry becomes increasingly important to urban air quality. However, the lifetime of individual organic nitrates and the reactions that lead to their production and removal remain relatively poorly constrained, causing organic nitrates to be poorly represented by models. Guided by recent laboratory and field studies, we developed a detailed gas-phase chemical mechanism representing most of the important individual organic nitrates. We use this mechanism within the Weather Research and Forecasting (WRF) model coupled with Chemistry (WRF-Chem) to describe the role of organic nitrates in nitrogen oxide chemistry and in comparisons to observations. We find the daytime lifetime of total organic nitrates with respect to all loss mechanisms to be 2.6 h in the model. This is consistent with analyses of observations at a rural site in central Alabama during the Southern Oxidant and Aerosol Study (SOAS) in summer 2013. The lifetime of the first-generation organic nitrates is ∼2 h versus the 3.2 h lifetime of secondary nitrates produced by oxidation of the first-generation nitrates. The different generations are subject to different losses, with dry deposition to the surface being the dominant loss process for the second-generation organic nitrates and chemical loss being dominant for the first-generation organic nitrates. Removal by hydrolysis is found to be responsible for the loss of ∼30  % of the total organic nitrate pool.

Description: Glyoxal (CHOCHO) is produced in the atmosphere by the oxidation of volatile organic compounds (VOCs). Like formaldehyde (HCHO), another VOC oxidation product, it is measurable from space by solar backscatter. Isoprene emitted by vegetation is the dominant source of CHOCHO and HCHO in most of the world. We use aircraft observations of CHOCHO and HCHO from the SENEX campaign over the southeast US in summer 2013 to better understand the CHOCHO time-dependent yield from isoprene oxidation, its dependence on nitrogen oxides (NOx  ≡  NO + NO2), the behavior of the CHOCHO–HCHO relationship, the quality of OMI CHOCHO satellite observations, and the implications for using CHOCHO observations from space as constraints on isoprene emissions. We simulate the SENEX and OMI observations with the Goddard Earth Observing System chemical transport model (GEOS-Chem) featuring a new chemical mechanism for CHOCHO formation from isoprene. The mechanism includes prompt CHOCHO formation under low-NOx conditions following the isomerization of the isoprene peroxy radical (ISOPO2). The SENEX observations provide support for this prompt CHOCHO formation pathway, and are generally consistent with the GEOS-Chem mechanism. Boundary layer CHOCHO and HCHO are strongly correlated in the observations and the model, with some departure under low-NOx conditions due to prompt CHOCHO formation. SENEX vertical profiles indicate a free-tropospheric CHOCHO background that is absent from the model. The OMI CHOCHO data provide some support for this free-tropospheric background and show southeast US enhancements consistent with the isoprene source but a factor of 2 too low. Part of this OMI bias is due to excessive surface reflectivities assumed in the retrieval. The OMI CHOCHO and HCHO seasonal data over the southeast US are tightly correlated and provide redundant proxies of isoprene emissions. Higher temporal resolution in future geostationary satellite observations may enable detection of the prompt CHOCHO production under low-NOx conditions apparent in the SENEX data.