Key Role of Equilibrium HONO Concentration over the Soil 

2021 ◽  
Author(s):  
Fengxia Bao ◽  
Hang Su ◽  
Uwe Kuhn ◽  
Yafang Cheng
Keyword(s):  
Gas Phase ◽  
Hydroxyl Radicals ◽  
Nitrous Acid ◽  
Measurement Method ◽  
Oxidative Capacity ◽  
Sources And Sinks ◽  
Dynamic Chamber ◽  
Open Question ◽  
Actinic Radiation

<p>Nitrous acid (HONO) is an important component of the nitrogen cycle. HONO can also be rapidly photolyzed by actinic radiation to form hydroxyl radicals (OH) and exerts a primary influence on the oxidative capacity of the atmosphere. The sources and sinks of HONO, however, are not fully understood. Soil nitrite, produced via nitrification or denitrification, is an important source for the atmospheric HONO production. [HONO]*, the equilibrium gas phase HONO concentration over the soil, has been suggested as key to understanding the environmental effects of soil fluxes of HONO (Su et al., 2011). But if and how [HONO]* may exist and vary remains an open question. In this project, a measurement method using a dynamic chamber has been developed to derive [HONO]* and the atmospheric soil fluxes of HONO can accordingly be quantified. We demonstrate the existence of [HONO]* and determine its variation in the course of soil drying processes. We show that when [HONO]* is higher than the atmospheric HONO concentration, HONO will be released from soil; otherwise, HONO will be deposited on soil. This work advances the understanding of soil HONO emissions, and the evaluation of its impact on the atmospheric oxidizing capacity and the nitrogen cycling.</p>

Coupling between the Tropospheric Photochemistry of Nitrous Acid (HONO) and Nitric Acid (HNO3)

2006 ◽  
Vol 3 (1) ◽  
pp. 31 ◽  
Author(s):  
Kevin C. Clemitshaw
Keyword(s):  
Nitric Acid ◽  
Hydroxyl Radicals ◽  
Nitrous Acid ◽  
Snow Pack ◽  
Rural And Remote ◽  
Sources And Sinks ◽  
Tropospheric Photochemistry ◽  
Recent Developments ◽  
Urban Rural ◽  
And Migration

Environmental Context.Nitrous acid (HONO) is formed in the troposphere in urban, rural and remote environments via several uncertain heterogeneous and photochemical processes that involve nitric acid (HNO3). A recently recognised process is initiated by the deposition and migration of HNO3 within snow-pack surfaces to form nitrate anions (NO3−). Photo-reduction of NO3− followed by acidification of the nitrite (NO2−) photo-product leads to emissions of gas-phase HONO. Seasonal observations at Halley, Antarctica are consistent with the formation of HONO via this process, which is potentially of global significance because much of the Earth’s land (and sea) surface is covered with snow and is sunlit for much of the year. Both HONO and HNO3 significantly influence the production of ozone (O3), which acts as a greenhouse gas in the troposphere, via their respective roles as a source of hydroxyl radicals (OH•) and as a sink for OH• and nitrogen dioxide (NO2). Abstract.The tropospheric photochemistry of nitrous acid (HONO) and its coupling with that of nitric acid (HNO3) in urban, rural and remote atmospheres are highlighted in terms of established and uncertain homogeneous and heterogeneous sources and sinks, together with known and potential effects and impacts. Observations made at Halley, Antarctica, via optical detection of an azo dye derivative of HONO are consistent with snow-pack photochemical production of HONO, which has potential significance for the production of hydroxyl radicals (OH•) and ozone (O3) on regional and global scales. Recent developments in measurement methods for HONO and HNO3 are also highlighted. It is now timely to conduct a formal intercomparison of the methods in order to evaluate and enhance their capabilities, and to validate the growing body of HONO and HNO3 data obtained in urban, rural and remote locations.

Photo-Induced Heterogeneous Chemistry of Reactive Species on Aerosol Surfaces: Using Photo-Fragmentation Laser Induced Fluorescence for the Measurement of Nitrous Acid Production from Titanium Dioxide Aerosols

2020 ◽  
Author(s):  
Joanna Dyson ◽  
Graham Boustead ◽  
Lauren Fleming ◽  
Mark Blitz ◽  
Daniel Stone ◽  
...  
Keyword(s):  
Atmospheric Chemistry ◽  
Nitrous Acid ◽  
Laser Induced Fluorescence ◽  
Heterogeneous Chemistry ◽  
Sources And Sinks ◽  
Atmospheric Species ◽  
Highly Sensitive ◽  
Secondary Pollutants ◽  
Reactive Uptake Coefficient

<p>The hydroxyl radical (OH) is the main oxidant in the troposphere and is vitally important for its role in the removal of greenhouse gases such as methane from the atmosphere. Moreover, the OH radical also has a role in the formation of secondary pollutants such as tropospheric ozone and secondary organic aerosols (SOAs), formed via the oxidation of volatile organic compounds (VOCs). Understanding the sources and sinks of OH within the atmosphere is therefore crucial in order to fully understand the concentration and distribution of trace atmospheric species associated with climate change and poor air quality.</p><p>In polluted environments the dominant source of OH to initiate oxidation is the photolysis of nitrous acid (HONO). Current atmospheric chemistry models underestimate the concentration of HONO indicating a potential missing tropospheric source of HONO. There is a large uncertainty in the production of HONO from the contribution and role of aerosols and heterogeneous chemistry both under light and dark conditions.</p><p>In order to investigate the missing source of HONO from illuminated aerosols and determine its atmospheric relevance, a photo-fragmentation laser induced fluorescence (PF-LIF) instrument coupled to an aerosol flow tube system has been constructed. The PF-LIF instrument provides a highly sensitive measurement of HONO by fragmenting it into OH which is then detected in a low pressure cell by LIF. The aim of this system is to measure the rate of production of HONO from illuminated aerosol surfaces.</p><p>We will present an overview of the PF-LIF instrument and results from experiments investigating the reactive uptake of NO<sub>2</sub> by TiO<sub>2</sub> aerosols to produce HONO. The change in the reactive uptake coefficient as a function of NO<sub>2</sub> concentration and the dependence of HONO production on relative humidity and light intensity will also be discussed.   </p>

scholarly journals Technical Note: Conversion of Isoprene Hydroxy Hydroperoxides (ISOPOOH) on Metal Environmental Simulation Chamber Walls

2016 ◽  
Author(s):  
Anne-Kathrin Bernhammer ◽  
Martin Breitenlechner ◽  
Frank N. Keutsch ◽  
Armin Hansel ◽  
Keyword(s):  
Gas Phase ◽  
Technical Note ◽  
Heterogeneous Reactions ◽  
Oxidation Products ◽  
Chemical Mechanism ◽  
Stainless Steel Surface ◽  
Sources And Sinks ◽  
Environmental Surfaces ◽  
Isoprene Oxidation

Abstract. 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 (ISOPOOH). 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 modelled ISOPOOH concentrations are by a factor of 20 higher than the observed and methyl vinyl ketone (MVK) and methacrolein (MACR) concentrations are by a factor of up to 2 lower compared to observations, despite the artifact-free detection method. Addition of catalytic conversion of 1,2-ISOPOOH and 4,3-ISOPOOH to MVK and 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 not only be caused intra-instrumentally but also by the general experimental setup. The work described here extends the role of heterogeneous reactions affection 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.

scholarly journals Cisplatin-induced hydroxyl radicals mediate pro-survival autophagy in human lung cancer H460 cells

2021 ◽  
Vol 54 (1) ◽  
Author(s):  
Somruethai Sumkhemthong ◽  
Eakachai Prompetchara ◽  
Pithi Chanvorachote ◽  
Chatchai Chaotham
Keyword(s):  
Lung Cancer ◽  
Hydroxyl Radicals ◽  
Human Lung ◽  
Human Lung Cancer ◽  
Radical Scavenger ◽  
Apoptosis Resistance ◽  
Lung Cancer Patients ◽  
Human Lung Cancer Cells ◽  
H460 Cells

Abstract Background Accumulated evidence demonstrates cisplatin, a recommended chemotherapy, modulating pro-survival autophagic response that contributes to treatment failure in lung cancer patients. However, distinct mechanisms involved in cisplatin-induced autophagy in human lung cancer cells are still unclear. Results Herein, role of autophagy in cisplatin resistance was indicated by a decreased cell viability and increased apoptosis in lung cancer H460 cells pre-incubated with wortmannin, an autophagy inhibitor, prior to treatment with 50 µM cisplatin for 24 h. The elevated level of hydroxyl radicals detected via flow-cytometry corresponded to autophagic response, as evidenced by the formation of autophagosomes and autolysosomes in cisplatin-treated cells. Interestingly, apoptosis resistance, autophagosome formation, and the alteration of the autophagic markers, LC3-II/LC3-I and p62, as well as autophagy-regulating proteins Atg7 and Atg3, induced by cisplatin was abrogated by pretreatment of H460 cells with deferoxamine, a specific hydroxyl radical scavenger. The modulations in autophagic response were also indicated in the cells treated with hydroxyl radicals generated via Fenton reaction, and likewise inhibited by pretreatment with deferoxamine. Conclusions In summary, the possible role of hydroxyl radicals as a key mediator in the autophagic response to cisplatin treatment, which was firstly revealed in this study would benefit for the further development of novel therapies for lung cancer.

scholarly journals The role of radiolysis in the modelling of C2H4O2 isomers and dimethyl ether in cold dark clouds

2020 ◽  
Vol 500 (3) ◽  
pp. 3414-3424
Author(s):  
Alec Paulive ◽  
Christopher N Shingledecker ◽  
Eric Herbst
Keyword(s):  
Gas Phase ◽  
Dimethyl Ether ◽  
Recent Observation ◽  
Cosmic Ray ◽  
Thermal Method ◽  
Dark Clouds ◽  
Ice Surface ◽  
Dust Grain ◽  
Complex Organic

ABSTRACT Complex organic molecules (COMs) have been detected in a variety of interstellar sources. The abundances of these COMs in warming sources can be explained by syntheses linked to increasing temperatures and densities, allowing quasi-thermal chemical reactions to occur rapidly enough to produce observable amounts of COMs, both in the gas phase, and upon dust grain ice mantles. The COMs produced on grains then become gaseous as the temperature increases sufficiently to allow their thermal desorption. The recent observation of gaseous COMs in cold sources has not been fully explained by these gas-phase and dust grain production routes. Radiolysis chemistry is a possible non-thermal method of producing COMs in cold dark clouds. This new method greatly increases the modelled abundance of selected COMs upon the ice surface and within the ice mantle due to excitation and ionization events from cosmic ray bombardment. We examine the effect of radiolysis on three C2H4O2 isomers – methyl formate (HCOOCH3), glycolaldehyde (HCOCH2OH), and acetic acid (CH3COOH) – and a chemically similar molecule, dimethyl ether (CH3OCH3), in cold dark clouds. We then compare our modelled gaseous abundances with observed abundances in TMC-1, L1689B, and B1-b.

Quantifying sources and sinks of trace gases using space-borne measurements: current and future science

2008 ◽  
Vol 366 (1885) ◽  
pp. 4509-4528 ◽  
Author(s):  
Paul I Palmer
Keyword(s):  
Trace Gases ◽  
Lower Troposphere ◽  
Biological Interactions ◽  
Satellite Measurements ◽  
Sources And Sinks ◽  
The Past ◽  
Fundamental Understanding ◽  
Earth’S Climate ◽  
New Generation

We have been observing the Earth's upper atmosphere from space for several decades, but only over the past decade has the necessary technology begun to match our desire to observe surface air pollutants and climate-relevant trace gases in the lower troposphere, where we live and breathe. A new generation of Earth-observing satellites, capable of probing the lower troposphere, are already orbiting hundreds of kilometres above the Earth's surface with several more ready for launch or in the planning stages. Consequently, this is one of the most exciting times for the Earth system scientists who study the countless current-day physical, chemical and biological interactions between the Earth's land, ocean and atmosphere. First, I briefly review the theory behind measuring the atmosphere from space, and how these data can be used to infer surface sources and sinks of trace gases. I then present some of the science highlights associated with these data and how they can be used to improve fundamental understanding of the Earth's climate system. I conclude the paper by discussing the future role of satellite measurements of tropospheric trace gases in mitigating surface air pollution and carbon trading.

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