Revisiting the reaction of dicarbonyls in aerosol proxy solutions containing ammonia: the case of butenedial

Reactions in aqueous solutions containing dicarbonyls (especially the α-dicarbonyls methylglyoxal, glyoxal, and biacetyl) and reduced nitrogen (NHx) have been studied extensively. It has been proposed that accretion reactions from dicarbonyls and NHx could be a source of particulate matter and brown carbon in the atmosphere and therefore have direct implications for human health and climate. Other dicarbonyls, such as the 1,4-unsaturated dialdehyde butenedial, are also produced from the atmospheric oxidation of volatile organic compounds, especially aromatics and furans, but their aqueous-phase reactions with NHx have not been characterized. In this work, we determine a pH-dependent mechanism of butenedial reactions in aqueous solutions with NHx that is compared to α-dicarbonyls, in particular the dialdehyde glyoxal. Similar to glyoxal, butenedial is strongly hydrated in aqueous solutions. Butenedial reaction with NHx also produces nitrogen-containing rings and leads to accretion reactions that form brown carbon. Despite glyoxal and butenedial both being dialdehydes, butenedial is observed to have three significant differences in its chemical behavior: (1) as previously shown, butenedial does not substantially form acetal oligomers, (2) the butenedial/OH− reaction leads to light-absorbing compounds, and (3) the butenedial/NHx reaction is fast and first order in the dialdehyde. Building off of a complementary study on butenedial gas-particle partitioning, we suggest that the behavior of other reactive dialdehydes and dicarbonyls may not always be adequately predicted by α-dicarbonyls, even though their dominant functionalities are closely related. The carbon skeleton (e.g., its hydrophobicity, length, and bond structure) also governs the fate and climate-relevant properties of dicarbonyls in the atmosphere. If other dicarbonyls behave like butenedial, their reaction with NHx could constitute a regional source of brown carbon to the atmosphere.

Revisiting the reaction of dicarbonyls in aerosol proxy solutions containing ammonia: the case of butenedial

Reactions in aqueous solutions containing dicarbonyls (especially the α-dicarbonyls methylglyoxal, glyoxal, and biacetyl) and reduced nitrogen (NHx) have been studied extensively. It has been proposed that accretion reactions from dicarbonyls and NHx could be a source of particulate matter and brown carbon in the atmosphere and therefore have direct implications for human health and climate. Other dicarbonyls, such as the 1,4-unsaturated dialdehyde butenedial, are also produced from the atmospheric oxidation of volatile organic compounds, especially aromatics and furans, but their aqueous phase reactions with NHx have not been characterized. In this work, we determine a pH-dependent mechanism of butenedial reactions in aqueous solutions with NHx that is compared to α-dicarbonyls, in particular the dialdehyde glyoxal. Similar to glyoxal, butenedial is strongly hydrated in aqueous solutions. Butenedial reaction with NHx also produces nitrogen-containing rings and leads to accretion reactions that form brown carbon. Despite glyoxal and butenedial both being dialdehydes, butenedial is observed to have three significant differences in its chemical behavior: (1) as previously shown, butenedial does not substantially form acetal oligomers, (2) the butenedial/OH− reaction leads to light-absorbing compounds, and (3) the butenedial/NHx reaction is fast and first order in the dialdehyde. Building off of a complementary study on butenedial gas-particle partitioning, we suggest that the behavior of other reactive dialdehydes and dicarbonyls may not always be adequately predicted by α-dicarbonyls, even though their dominant functionalities are closely related. The carbon skeleton (e.g., its hydrophobicity, length, and bond structure) also governs the fate and climate-relevant properties of dicarbonyls in the atmosphere. If other dicarbonyls behave like butenedial, their reaction with NHx could constitute a regional source of brown carbon to the atmosphere.

THE NAME-LIST OF THE 1701 CENSUS BOOK OF THE TARA REGION: COMPOSITION, VARIABILITY, STATISTICS

The material for the study is a historical regional source of a fiscal nature. The system of personal names is considered as an obligatory component of the naming of Siberian taxpayers at the turn of the 17th–18th centuries. The system of male and female names of the Census Book is revealed. The phonetic, grammatical, and derivational variability of modified and unmodified names is characterized. The frequency of personal nominations is determined.

Daily Variability in the Terrestrial UV Airglow

New capability for observing conditions in the upper atmosphere comes with the implementation of global ultraviolet (UV) imaging from geosynchronous orbit. Observed by the NASA GOLD mission, the emissions of atomic oxygen (OI) and molecular nitrogen (N2) in the 133–168-nm range can be used to characterize the behavior of these major constituents of the thermosphere. Observations in the ultraviolet from the first 200 days of 2019 indicate that the oxygen emission at 135.6 nm varies much differently than the broader Lyman-Birge-Hopfield (LBH) emission of N2. This is determined from monitoring the average instrument response from two roughly 1000 km2 areas, well separated from one another, at the same time of each day. Variations in the GOLD response to UV emissions in the monitored regions are determined, both in absolute terms and relative to a running 7-day average of GOLD measurements. We find that variations in N2 emissions in the two separate regions are significantly correlated, while oxygen emissions, observed in the same fixed geographic regions at the same universal time each day, exhibit a much lower correlation, and exhibit no correlation with the N2 emissions in the same regions. This indicates that oxygen densities in the airglow-originating altitude range of 150–200 km vary independently from the variations in nitrogen, which are so well correlated across the dayside to suggest a direct connection to variation in solar extreme-UV flux. The relation of the atomic oxygen variations to solar and geomagnetic activity is also shown to be low, suggesting the existence of a regional source that modifies the production of atomic oxygen in the thermosphere.