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: Oxidation of organic compounds in the atmosphere produces an immensely complex mixture of product species, posing a challenge for both their measurement in laboratory studies and their inclusion in air quality and climate models. Mass spectrometry techniques can measure thousands of these species, giving insight into these chemical processes, but the datasets themselves are highly complex. Data reduction techniques that group compounds in a chemically and kinetically meaningful way provide a route to simplify the chemistry of these systems but have not been systematically investigated. Here we evaluate three approaches to reducing the dimensionality of oxidation systems measured in an environmental chamber: positive matrix factorization (PMF), hierarchical clustering analysis (HCA), and a parameterization to describe kinetics in terms of multigenerational chemistry (gamma kinetics parameterization, GKP). The evaluation is implemented by means of two datasets: synthetic data consisting of a three-generation oxidation system with known rate constants, generation numbers, and chemical pathways; and the measured products of OH-initiated oxidation of a substituted aromatic compound in a chamber experiment. We find that PMF accounts for changes in the average composition of all products during specific periods of time but does not sort compounds into generations or by another reproducible chemical process. HCA, on the other hand, can identify major groups of ions and patterns of behavior and maintains bulk chemical properties like carbon oxidation state that can be useful for modeling. The continuum of kinetic behavior observed in a typical chamber experiment can be parameterized by fitting species' time traces to the GKP, which approximates the chemistry as a linear, first-order kinetic system. The fitted parameters for each species are the number of reaction steps with OH needed to produce the species (the generation) and an effective kinetic rate constant that describes the formation and loss rates of the species. The thousands of species detected in a typical laboratory chamber experiment can be organized into a much smaller number (10–30) of groups, each of which has a characteristic chemical composition and kinetic behavior. This quantitative relationship between chemical and kinetic characteristics, and the significant reduction in the complexity of the system, provides an approach to understanding broad patterns of behavior in oxidation systems and could be exploited for mechanism development and atmospheric chemistry modeling.

Description: To achieve high-precision and reproducible results from radiocarbon (14C) dating of carbonate samples in paleoclimate research, a new CO2 extraction line was designed, constructed, and characterized at the Heidelberg Radiocarbon Lab of the Institute of Environmental Physics, Heidelberg. The setup includes a circular glass-tube design, which is operated at vacuum pressure levels of the order of 10–5 mbar. The efficiency of the extraction process was assessed, showing significantly favorable conditions for solid piece samples (99.58 ± 4.69)% over powdered samples (88.28 ± 10.03)%. Process blank values are below 0.2 pMC apparent 14C activity. Repeated measurements of IAEA C2 standards with an average value of (41.09 ± 0.23) pMC attest high accuracy and reproducibility of the instrument. Six consecutive samples of 6 to 12 mg carbonate mass can be processed in one run of roughly 2.5 hours. Thus, the new setup contributes to time-efficient and reproducible radiocarbon dating results for paleoclimate research at the Institute of Environmental Physics. In a first application, Dead Carbon Fraction (DCF) values of a Holocene alpine stalagmite from Schratten Cave are presented, revealing extraordinarily high offsets between atmospheric and stalagmite 14C with DCF values between (49.4 ± 0.4)% and (61.6 ± 0.4)%.

Description: Short-lived highly reactive atmospheric species, such as organic peroxy radicals (RO2) and stabilized Criegee intermediates (SCIs), play an important role in controlling the oxidative removal and transformation of many natural and anthropogenic trace gases in the atmosphere. Direct speciated measurements of these components are extremely helpful for understanding their atmospheric fate and impact. We describe the development of an online method for measurements of SCIs and RO2 in laboratory experiments using chemical derivatization and spin trapping techniques combined with H3O+ and NH4+ chemical ionization mass spectrometry (CIMS). Using chemical derivatization agents with low proton affinity, such as electron-poor carbonyls, we scavenge all SCIs produced from a wide range of alkenes without depleting CIMS reagent ions. Comparison between our measurements and results from numeric modeling, using a modified version of the Master Chemical Mechanism, shows that the method can be used for the quantification of SCIs in laboratory experiments with a detection limit of 1.4×107 molecule cm−3 for an integration time of 30 s with the instrumentation used in this study. We show that spin traps are highly reactive towards atmospheric radicals and form stable adducts with them by studying the gas-phase kinetics of the reaction of spin traps with the hydroxyl radical (OH). We also demonstrate that spin trap adducts with SCIs and RO2 can be simultaneously probed and quantified under laboratory conditions with a detection limit of 1.6×108 molecule cm−3 for an integration time of 30 s for RO2 species with the instrumentation used in this study. Spin trapping prevents radical secondary reactions and cycling, ensuring that measurements are not biased by chemical interferences, and it can be implemented for detecting RO2 species in laboratory studies and potentially in the ambient atmosphere.