Cryptogamic organisms are a substantial source and sink for volatile organic compounds in the Amazon region

Cryptogamic organisms such as bryophytes and lichens cover most surfaces within tropical forests, yet their impact on the emission of biogenic volatile organic compounds is unknown. These compounds can strongly influence atmospheric oxidant levels as well as secondary organic aerosol concentrations, and forest canopy leaves have been considered the dominant source of these emissions. Here we present cuvette flux measurements, made in the Amazon rainforest between 2016–2018, and show that common bryophytes emit large quantities of highly reactive sesquiterpenoids and that widespread lichens strongly uptake atmospheric oxidation products. A spatial upscaling approach revealed that cryptogamic organisms emit sesquiterpenoids in quantities comparable to current canopy attributed estimates, and take up atmospheric oxidation products at rates comparable to hydroxyl radical chemistry. We conclude that cryptogamic organisms play an important and hitherto overlooked role in atmospheric chemistry above and within tropical rainforests.

Towards a Comprehensive Characterization of the Low-Temperature Autoxidation of Di-n-Butyl Ether

In the present study, we investigated the oxidation of 2500 ppm of di-n-butyl ether under fuel-rich conditions (φ = 2) at low temperatures (460–780 K), a residence time of 1 s, and 10 atm. The experiments were carried out in a fused silica jet-stirred reactor. Oxidation products were identified and quantified in gas samples by gas chromatography and Fourier transform infrared spectrometry. Samples were also trapped through bubbling in cool acetonitrile for high-pressure liquid chromatography (HPLC) analyses. 2,4-dinitro-phenylhydrazine was used to derivatize carbonyl products and distinguish them from other isomers. HPLC coupled to high resolution mass spectrometry (Orbitrap Q-Exactive®) allowed for the detection of oxygenated species never observed before, i.e., low-temperature oxidation products (C8H12O4,6, C8H16O3,5,7, and C8H18O2,5) and species that are more specific products of atmospheric oxidation, i.e., C16H34O4, C11H24O3, C11H22O3, and C10H22O3. Flow injection analyses indicated the presence of high molecular weight oxygenated products (m/z > 550). These results highlight the strong similitude in terms of classes of oxidation products of combustion and atmospheric oxidation, and through autoxidation processes. A kinetic modeling of the present experiments indicated some discrepancies with the present data.

High atmospheric oxidation capacity drives wintertime nitrate pollution in the eastern Yangtze River Delta of China

Nitrate aerosol plays an increasingly important role in wintertime haze pollution in China. Despite intensive research on the wintertime nitrate chemistry in recent years, quantitative constraints on the formation mechanisms of nitrate aerosol in the Yangtze River Delta (YRD), one of the most developed and densely populated regions in eastern China, remain inadequate. In this study, we identify the major nitrate formation pathways and their key controlling factors during the winter haze pollution period in the eastern YRD using two-year (2018–2019) field observations and detailed observation-constrained model simulations. We find that the high atmospheric oxidation capacity, coupled with high aerosol liquid water content (ALWC), made both the heterogeneous hydrolysis of dinitrogen pentoxide (N2O5) and the gas-phase OH oxidation of nitrogen dioxide (NO2) important pathways for wintertime nitrate formation in this region, with contribution percentages of 69 % and 29 % in urban areas and 63 % and 35 % in suburban areas, respectively. We further find that the gas-to-particle partitioning of nitric acid (HNO3) was very efficient so that the rate-determining step in the overall formation process of nitrate aerosol was the oxidation of NOx to HNO3 through both heterogeneous and gas-phase processes. The atmospheric oxidation capacity (i.e., the availability of O3 and OH radicals) was the key factor controlling the production rate of HNO3 from both processes. During the COVID-19 lockdown (January–February 2020), the enhanced atmospheric oxidation capacity greatly promoted the oxidation of NOx to nitrate and hence weakened the response of nitrate aerosol to the emission reductions in urban areas. Our study sheds light on the detailed formation mechanisms of wintertime nitrate aerosol in the eastern YRD and highlights the demand for the synergetic regulation of atmospheric oxidation capacity and NOx emissions to mitigate wintertime nitrate and haze pollution in eastern China.

Atmospheric oxidation capacity and ozone pollution mechanism in a coastal city of Southeast China: Analysis of a typical photochemical episode by Observation-Based Model

A typical multi-day ozone (O3) pollution event was chosen to explore the atmospheric oxidation capacity (AOC), OH reactivity, radical chemistry, and O3 pollution mechanism in a coastal city of Southeast China, with an Observation-Based Model coupled to the Master Chemical Mechanism (OBM-MCM). The hydroxyl radical (OH) was the predominant oxidant (91±23 %) for daytime AOC, while NO3 radical played an important role for AOC during the nighttime (64±11 %). Oxygenated volatile organic compounds (OVOCs, 30±8 %), NO2 (29±8 %) and CO (25±5 %) were the dominant contributors to OH reactivity, accelerating the production of O3 and recycling of ROx radicals (ROx=OH+HO2+RO2). Photolysis of nitrous acid (HONO, 33±14 %), O3 (25±13 %), formaldehyde (HCHO, 20±5 %), and other OVOCs (17±2 %) were the important primary sources of ROx radicals, which played initiation roles in atmospheric oxidation processes. O3 formation was VOC-sensitive, and controlling emissions of aromatics, alkenes, and long-chain alkanes were benefit for ozone pollution mitigation. Combined with regional transport analysis, the reasons for this O3 episode were the accumulation of local photochemical production and regional transport. The results of sensitivity analysis showed that VOCs were the limiting factor of radical recycling and O3 formation, and the 5 % reduction of O3 would be achieved by decreasing 20 % anthropogenic VOCs. The findings of this study have significant guidance for emission reduction and regional collaboration on future photochemical pollution control in the relatively clean coastal cities of China and similar countries.