Auswahl der wissenschaftlichen Literatur zum Thema „Reactive species HONO and HOBr“

Abstract. Near-total depletions of ozone have been observed in the Arctic spring since the mid 1980s. The autocatalytic cycles involving reactive halogens are now recognized to be of main importance for Ozone Depletion Events (ODEs) in the Polar Boundary Layer (PBL). We present sensitivity studies using the model MISTRA in the box-model mode on the influence of chemical species on these ozone depletion processes. In order to test the sensitivity of the chemistry under polar conditions, we compared base runs undergoing fluxes of either Br2, BrCl, or Cl2 to induce ozone depletions, with similar runs including a modification of the chemical conditions. The role of HCHO, H2O2, DMS, Cl2, C2H4, C2H6, HONO, NO2, and RONO2 was investigated. Cases with elevated mixing ratios of HCHO, H2O2, DMS, Cl2, and HONO induced a shift in bromine speciation from Br/BrO to HOBr/HBr, while high mixing ratios of C2H6 induced a shift from HOBr/HBr to Br/BrO. Cases with elevated mixing ratios of HONO, NO2, and RONO2 induced a shift to BrNO2/BrONO2. The shifts from Br/BrO to HOBr/HBr accelerated the aerosol debromination, but also increased the total amount of deposited bromine at the surface (mainly via increased deposition of HOBr). These shifts to HOBr/HBr also hindered the BrO self-reaction. In these cases, the ozone depletion was slowed down, where increases in H2O2 and HONO had the greatest effect. The tests with increased mixing ratios of C2H4 highlighted the decrease in HOx which reduced the production of HOBr from bromine radicals. In addition, the direct reaction of C2H4 with bromine atoms led to less available reactive bromine. The aerosol debromination was therefore strongly reduced. Ozone levels were highly affected by the chemistry of C2H4. Cl2-induced ozone depletions were found unrealistic compared to field measurements due to the rapid production of CH3O2, HOx, and ROOH which rapidly convert reactive chlorine to HCl in a "chlorine counter-cycle". This counter-cycle efficiently reduces the concentration of reactive halogens in the boundary layer. Depending on the relative bromine and chlorine mixing ratios, the production of CH3O2, HOx, and ROOH from the counter-cycle can significantly affect the bromine chemistry. Therefore, the presence of both bromine and chlorine in the air may unexpectedly lead to a slow down in ozone destruction. For all NOy species studied (HONO, NO2, RONO2) the chemistry is characterized by an increased bromine deposition on snow reducing the amount of reactive bromine in the air. Ozone is less depleted under conditions of high mixing ratios of NOx. The production of HNO3 led to the acid displacement of HCl, and the release of chlorine out of salt aerosols (Cl2 or BrCl) increased.

Abstract. Nitrous acid (HONO) plays an important role in the formation of ozone and fine aerosols in the urban atmosphere. In this study, a new simulation approach is presented to calculate the HONO mixing ratios using a deep neural technique based on measured variables. The Reactive Nitrogen Species using a Deep Neural Network (RND) simulation is implemented in Python. The first version of RND (RNDv1.0) is trained, validated, and tested with HONO measurement data obtained in Seoul, South Korea, from 2016 to 2021. RNDv1.0 is constructed using k-fold cross validation and evaluated with index of agreement, correlation coefficient, root mean squared error, and mean absolute error. The results show that RNDv1.0 adequately represents the main characteristics of the measured HONO, and it is thus proposed as a supplementary model for calculating the HONO mixing ratio in a polluted urban environment.

Myeloperoxidase (MPO), found mainly in neutrophils, is released in inflammation. MPO produces reactive halogen species (RHS), which are bactericidal agents. However, RHS overproduction, i.e., halogenative stress, can also damage host biomolecules, and MPO itself may be targeted by RHS. Therefore, we examined the susceptibility of MPO to inactivation by its primary products (HOCl, HOBr, HOSCN) and secondary products such as taurine monochloramine (TauCl) and taurine monobromamine (TauBr). MPO was dose-dependently inhibited up to complete inactivity by treatment with HOCl or HOBr. TauBr diminished the activity but did not eliminate it. TauCl had no effect. MPO became inactivated when producing HOCl or HOBr but not HOSCN. Taurine protected MPO against inactivation when MPO was catalyzing oxidation of Cl− to HOCl, whereas taurine failed to prevent inactivation when MPO was working with Br−, either alone or in combination with Cl−. SCN− interfered with HOCl-mediated MPO inhibition. UV–vis spectra showed that heme degradation is involved in HOCl- and HOBr-mediated MPO inactivation. A negative linear correlation between the remaining chlorinating activity of HOCl- or HOBr-modified MPO and Escherichia coli survival upon incubation with MPO/H2O2/Cl− was found. This study elucidated the possibility of MPO downregulation by MPO-derived RHS, which could counteract halogenative stress.

Reactive oxygen species (ROS) have been implicated in numerous pathological processes and their homeostasis facilitates the dynamic balance of intracellular redox states. Among ROS, hypobromous acid (HOBr) has a high similarity to hypochlorous acid (HOCl) in both chemical and physical properties, whereas it has received relatively little attention. Meanwhile, selective recognition of endogenous HOBr suffers great challenges due to the fact that the concentration of this molecule is much lower than that of HOCl. Fluorescence-based detection systems have emerged as very important tools to monitor biomolecules in living cells and organisms owing to distinct advantages, particularly the temporal and spatial sampling for in vivo imaging applications. To date, the development of HOBr-specific fluorescent probes is still proceeding quite slowly, and the research related to this area has not been systematically summarized. In this review, we are the first to review the progress made so far in fluorescent probes for selective recognition and detection of HOBr. The molecular structures, sensing mechanisms, and their successful applications of these probes as bioimaging agents are discussed here in detail. Importantly, we hope this review will call for more attention to this rising field, and that this could stimulate new future achievements.

Abstract. New techniques have recently been developed and applied to capture reactive nitrogen species, including nitrogen oxides (NOx=NO+NO2), nitrous acid (HONO), nitric acid (HNO3), and particulate nitrate (pNO3-), for accurate measurement of their isotopic composition. Here, we report – for the first time – the isotopic composition of HONO from biomass burning (BB) emissions collected during the Fire Influence on Regional to Global Environments Experiment (FIREX, later evolved into FIREX-AQ) at the Missoula Fire Science Laboratory in the fall of 2016. We used our newly developed annular denuder system (ADS), which was verified to completely capture HONO associated with BB in comparison with four other high-time-resolution concentration measurement techniques, including mist chamber–ion chromatography (MC–IC), open-path Fourier transform infrared spectroscopy (OP-FTIR), cavity-enhanced spectroscopy (CES), and proton-transfer-reaction time-of-flight mass spectrometry (PTR-ToF). In 20 “stack” fires (direct emission within ∼5 s of production by the fire) that burned various biomass materials from the western US, δ15N–NOx ranges from −4.3 ‰ to +7.0 ‰, falling near the middle of the range reported in previous work. The first measurements of δ15N–HONO and δ18O–HONO in biomass burning smoke reveal a range of −5.3 ‰ to +5.8 ‰ and +5.2 ‰ to +15.2 ‰, respectively. Both HONO and NOx are sourced from N in the biomass fuel, and δ15N–HONO and δ15N–NOx are strongly correlated (R2=0.89, p<0.001), suggesting HONO is directly formed via subsequent chain reactions of NOx emitted from biomass combustion. Only 5 of 20 pNO3- samples had a sufficient amount for isotopic analysis and showed δ15N and δ18O of pNO3- ranging from −10.6 ‰ to −7.4 ‰ and +11.5 ‰ to +14.8 ‰, respectively. Our δ15N of NOx, HONO, and pNO3- ranges can serve as important biomass burning source signatures, useful for constraining emissions of these species in environmental applications. The δ18O of HONO and NO3- obtained here verify that our method is capable of determining the oxygen isotopic composition in BB plumes. The δ18O values for both of these species reflect laboratory conditions (i.e., a lack of photochemistry) and would be expected to track with the influence of different oxidation pathways in real environments. The methods used in this study will be further applied in future field studies to quantitatively track reactive nitrogen cycling in fresh and aged western US wildfire plumes.

Abstract. Soil and biological soil crusts can emit nitrous acid (HONO) and nitric oxide (NO). The terrestrial ground surface in arid and semiarid regions is anticipated to play an important role in the local atmospheric HONO budget, deemed to represent one of the unaccounted-for HONO sources frequently observed in field studies. In this study HONO and NO emissions from a representative variety of soil and biological soil crust samples from the Mediterranean island Cyprus were investigated under controlled laboratory conditions. A wide range of fluxes was observed, ranging from 0.6 to 264 ng m−2 s−1 HONO-N at optimal soil water content (20–30 % of water holding capacity, WHC). Maximum NO-N fluxes at this WHC were lower (0.8–121 ng m−2 s−1). The highest emissions of both reactive nitrogen species were found from bare soil, followed by light and dark cyanobacteria-dominated biological soil crusts (biocrusts), correlating well with the sample nutrient levels (nitrite and nitrate). Extrapolations of lab-based HONO emission studies agree well with the unaccounted-for HONO source derived previously for the extensive CYPHEX field campaign, i.e., emissions from soil and biocrusts may essentially close the Cyprus HONO budget.

Abstract. The rate of production of HONO from illuminated TiO2 aerosols in the presence of NO2 was measured using an aerosol flow tube system coupled to a photo-fragmentation laser-induced fluorescence detection apparatus. The reactive uptake coefficient of NO2 to form HONO, γNO2→HONO, was determined for NO2 mixing ratios in the range 34–400 ppb, with γNO2→HONO spanning the range (9.97 ± 3.52) × 10−6 to (1.26 ± 0.17) × 10−4 at a relative humidity of 15 ± 1 % and for a lamp photon flux of (1.63 ± 0.09) ×1016 photons cm−2 s−1 (integrated between 290 and 400 nm), which is similar to midday ambient actinic flux values. γNO2→HONO increased as a function of NO2 mixing ratio at low NO2 before peaking at (1.26 ± 0.17) ×10-4 at ∼ 51 ppb NO2 and then sharply decreasing at higher NO2 mixing ratios rather than levelling off, which would be indicative of surface saturation. The dependence of HONO production on relative humidity was also investigated, with a peak in production of HONO from TiO2 aerosol surfaces found at ∼ 25 % RH. Possible mechanisms consistent with the observed trends in both the HONO production and reactive uptake coefficient were investigated using a zero-dimensional kinetic box model. The modelling studies supported a mechanism for HONO production on the aerosol surface involving two molecules of NO2, as well as a surface HONO loss mechanism which is dependent upon NO2. In a separate experiment, significant production of HONO was observed from illumination of mixed nitrate/TiO2 aerosols in the absence of NO2. However, no production of HONO was seen from the illumination of nitrate aerosols alone. The rate of production of HONO observed from mixed nitrate/TiO2 aerosols was scaled to ambient conditions found at the Cape Verde Atmospheric Observatory (CVAO) in the remote tropical marine boundary layer. The rate of HONO production from aerosol particulate nitrate photolysis containing a photocatalyst was found to be similar to the missing HONO production rate necessary to reproduce observed concentrations of HONO at CVAO. These results provide evidence that particulate nitrate photolysis may have a significant impact on the production of HONO and hence NOx in the marine boundary layer where mixed aerosols containing nitrate and a photocatalytic species such as TiO2, as found in dust, are present.

Abstract. Nitrous acid (HONO) and nitryl chloride (ClNO2) – through their photolysis – can have profound effects on the nitrogen cycle and oxidation capacity of the lower troposphere. Previous numerical studies have separately considered and investigated the sources/processes of these compounds and their roles in the fate of reactive nitrogen and the production of ozone (O3), but their combined impact on the chemistry of the lower part of the troposphere has not been addressed yet. In this study, we updated the WRF-Chem model with the currently known sources and chemistry of HONO and chlorine in a new chemical mechanism (CBMZ_ReNOM), and applied it to a study of the combined effects of HONO and ClNO2 on summertime O3 in the boundary layer over China. We simulated the spatial distributions of HONO, ClNO2, and related compounds at the surface and within the lower troposphere. The results showed that the modeled HONO levels reached up to 800–1800 ppt at the surface (0–30 m) over the North China Plain (NCP), the Yangtze River Delta (YRD), and the Pearl River Delta (PRD) regions and that HONO was concentrated within a 0–200 m layer. In comparison, the simulated surface ClNO2 mixing ratio was around 800–1500 ppt over the NCP, YRD, and central China regions and was predominantly present in a 0–600 m layer. HONO enhanced daytime ROx (OH + HO2 + RO2) and O3 at the surface (0–30 m) by 2.8–4.6 ppt (28–37 %) and 2.9–6.2 ppb (6–13 %), respectively, over the three most developed regions, whereas ClNO2 increased surface O3 in the NCP and YRD regions by 2.4–3.3 ppb (or 5–6 %) and it also had a significant impact (3–6 %) on above-surface O3 within 200–500 m. The combined effects increased surface O3 by 11.5, 13.5, and 13.3 % in the NCP, YRD, and PRD regions, respectively. Over the boundary layer (0–1000 m), the HONO and ClNO2 enhanced O3 by up to 5.1 and 3.2 %, respectively, and their combined effect increased O3 by 7.1–8.9 % in the three regions. The new module noticeably improved O3 predictions at ∼ 900 monitoring stations throughout China by reducing the mean bias from −4.3 to 0.1 ppb. Our study suggests the importance of considering these reactive nitrogen species simultaneously into chemical transport models to better simulate the formation of summertime O3 in polluted regions.

Abstract. We report on applications of the ultraviolet-light-emitting-diode-based incoherent broadband cavity-enhanced absorption spectroscopy (UV-LED-IBBCEAS) technique for optical monitoring of HONO, NO2 and CH2O in a simulation chamber. Performance intercomparison of UV-LED-IBBCEAS with a wet chemistry-based NitroMAC sensor and a Fourier transform infrared (FTIR) spectrometer has been carried out on real-time simultaneous measurement of HONO, NO2 and CH2O concentrations during the reaction of NO2 with H2O vapour in CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber). The 1σ (signal-to-noise ratio (SNR) = 1) detection limits of 112 pptv for NO2, 56 pptv for HONO and 41 ppbv for CH2O over 120 s were found for the UV-LED-IBBCEAS measurement. On the contrary to many set-ups where cavities are installed outside the simulation chamber, we describe here an original in situ permanent installation. The intercomparison results demonstrate that IBBCEAS is a very well suitable technique for in situ simultaneous measurements of multiple chemically reactive species with high sensitivity and high precision even if the absorption bands of these species are overlapped. It offers excellent capacity for non-invasive optical monitoring of chemical reactions without any perturbation. For the application to simulation chambers, it has the advantage to provide a spatially integrated measurement across the reactor and hence to avoid point-sampling-related artefacts.

MPO (myeloperoxidase) catalyses the oxidation of chloride, bromide and thiocyanate by hydrogen peroxide to HOCl (hypochlorous acid), HOBr (hypobromous acid) and HOSCN (hypothiocyanous acid) respectively. Specificity constants indicate that SCN− is a major substrate for MPO. HOSCN is also a major oxidant generated by other peroxidases including salivary, gastric and eosinophil peroxidases. While HOCl and HOBr are powerful oxidizing agents, HOSCN is a less reactive, but more specific, oxidant which targets thiols and especially low pKa species. In the present study we show that HOSCN targets cysteine residues present in PTPs (protein tyrosine phosphatases) with this resulting in a loss of PTP activity for the isolated enzyme, in cell lysates and intact J774A.1 macrophage-like cells. Inhibition also occurs with MPO-generated HOCl and HOBr, but is more marked with MPO-generated HOSCN, particularly at longer incubation times. This inhibition is reversed by dithiothreitol, particularly at early time points, consistent with the reversible oxidation of the active site cysteine residue to give either a cysteine–SCN adduct or a sulfenic acid. Inhibition of PTP activity is associated with increased phosphorylation of p38a and ERK2 (extracellular-signal-regulated kinase 2) as detected by Western blot analysis and phosphoprotein arrays, and results in altered MAPK (mitogen-activated protein kinase) signalling. These data indicate that the highly selective targeting of some protein thiols by HOSCN can result in perturbation of cellular phosphorylation and altered cell signalling. These changes occur with (patho)physiological concentrations of SCN− ions, and implicate HOSCN as an important mediator of inflammation-induced oxidative damage, particularly in smokers who have elevated plasma levels of SCN−.

La mesure des concentrations d'espèces traces, susceptibles d'avoir un impact notable sur la santé, le climat ou la stabilité de la couche d'ozone constitue un véritable défi. Les prochaines missions spatiales, prévues à haute sensibilité (FORUM et IASI-NG), apporteront un progrès seulement si les paramètres spectraux nécessaires sont disponibles. Pour certaines espèces réactives, telles que l'acide nitreux (HONO) et l'acide hypobromeux (HOBr), les données spectroscopiques sont incomplètes ou quasiment inexistantes. Le défi dans cette thèse consiste à obtenir des paramètres spectroscopiques quantitatifs pour ces espèces. Pour atteindre cet objectif, un dispositif instrumental novateur impliquant l'utilisation simultanée de deux instruments, une expérience IR/THz, a été construit : une cellule thermostatée (200-350K) conçue en matériaux inertes, verre et téflon, est combinée à un spectromètre THz dans la région 0.1-1.1 THz et un spectromètre à Transformée de Fourier (FTS) à haute résolution (HR) dans le domaine IR. Le spectromètre THz permet de sélectionner plusieurs raies purement rotationnelles de la molécule cible pour la détermination de la pression partielle et le FTS la mesure simultanée du spectre rovibrationnel dans une fenêtre atmosphérique IR utilisable pour la quantification de l'espèce d'intérêt. La stratégie s'appuie donc sur le fait que les intensités des raies de rotation pure dépendent uniquement du moment dipolaire moléculaire, qui est connu avec précision à partir de mesures existantes par effet Stark. Dans le cas de HONO qui n'existe au laboratoire que sous la forme d'un équilibre avec H2O, NO et NO2, la méconnaissance de la pression partielle dans le mélange gazeux entraîne de sérieuses difficultés pour effectuer des mesures quantitatives. De plus, HONO possède deux formes isomériques et la hauteur de la barrière d'isomérisation entre le cis- et le trans-HONO DeltaCis-Trans est encore mal connue, ce qui affecte les positions et surtout les intensités de raies. Pour obtenir une valeur plus précise de cette barrière, des spectres ont été enregistrés à HR dans la gamme 50 - 200 cm-1, à 3 températures (240, 270 et 296 K), en utilisant le rayonnement synchrotron de la ligne AILES à SOLEIL. Des modélisations précises ont été effectuées et ont permis de déterminer la hauteur de la barrière DeltaCis-Trans = 95.8 ± 9.2 cm-1. Notre valeur est en bon accord avec la détermination précédente de Sironneau et al. (99 ± 25 cm-1) mais nous avons amélioré la précision d'un facteur 2.6. Nous avons utilisé cette nouvelle valeur de DeltaCis-Trans et les paramètres du moment dipolaire pour un calcul du spectre synthétique. Une liste de raies précise dans la région de l'IR lointain (0 - 200 cm-1) incluant les positions et intensités absolues a été compilée et s'est avérée plus robuste pour une meilleure détection de HONO dans les objets astrophysiques. Pour la détermination des intensités absolues dans la région IR moyen où HONO est actuellement détectée, des spectres simultanés IR/THz ont été enregistrés au LISA en utilisant l'instrumentation innovante développée durant cette thèse. Une première modélisation de ces spectres est présentée dans cette thèse et in fine, il en découlera une liste de raies pour HONO dans la région 730 - 920 cm-1 qui sera fourni à la communauté scientifique via les bases de données HITRAN et GEISA et exploitée dans l'analyse des observations satellitaires. Concernant HOBr, l'objectif sera de compiler une base de données spectroscopiques dans l'IR vers 8.6 um qui sera utilisée par IASI-NG et FORUM pour une détection et quantification dans l'atmosphère terrestre. Notons que HOBr joue un rôle important dans la chimie atmosphérique et n'existe au laboratoire que dans un mélange caractérisé par l'équilibre chimique : H2O + Br2O = 2(HOBr). La méthodologie et les outils expérimentaux développés durant cette thèse sont un atout pour la mise en oeuvre de ce projet qui, constitue les perspectives de ce travail
Measuring trace gases having a notable impact on human health, climate and the stability of the ozone layer constitutes an extremely important challenge. In the coming years, new, higher sensitivity satellite instruments will improve atmospheric sounding only if the necessary spectral parameters are available. For some species of atmospheric interest such as nitrous acid (HONO) and hypobromous acid (HOBr), spectroscopic data are incomplete or almost non-existent. The challenge in this thesis is to get quantitative spectroscopic parameters for these species. To achieve this objective, an innovative instrumental set-up involving the simultaneous use of two instruments, an IR/THz dual beam experiment, has been built: a thermostatically controlled cell (200-350K) made of inert materials, glass and Teflon, capable of accommodating a 0.1-1.1 THz spectrometer and coupled to a high resolution (HR) Fourier Transform spectrometer (FTS) in the IR range. The THz spectrometer allows to select rotational lines of the target molecule for partial pressure determination, and the FTS enables simultaneous measurement of the rovibrational spectrum in an IR atmospheric window for quantification of the species of interest. The adopted strategy relies on the fact that the intensities of the rotational spectra simply depend on the permanent dipole moment of the molecule of interest, determined with high accuracy from Stark effect measurements. In the case of HONO, which only exists in laboratory conditions in the form of an equilibrium mixture with other species like H2O, NO and NO2, the lack of knowledge of the partial pressure in the gas mixture leads to serious difficulties for quantitative measurements. In addition, HONO exists in two conformer forms, and the height of the conformer barrier between cis- and trans-HONO DeltaCis-Trans is still poorly known, which affects lines positions and especially lines intensities. To improve the determination of the energy difference between the ground vibrational state of the cis- and trans-HONO conformers of HONO, high resolution spectra were recorded in the 50-200 cm-1 spectral region at three different temperatures (240, 270 and 296 K), using the synchrotron radiation of the AILES beamline at SOLEIL. Precise modelling has been performed and were used to determine the height of the conformer barrier DeltaCis-Trans = 95.8 ± 9.2 cm-1. Our value is in good agreement with the previous determination by Sironneau et al (99 ± 25 cm-1), but we have improved the accuracy of this determination by a factor of 2.6. We used this new value of DeltaCis-Trans and the dipole moment parameters for a synthetic spectrum calculation. A precise line list in the far-IR region (0 - 200 cm-1), including positions and absolute lines intensities was generated and, proved to be more robust for an improved detection of HONO in astrophysical objects. To determine absolute intensities in the mid-IR region where HONO is currently detected, simultaneous IR/THz spectra were recorded at LISA using innovative instrumentation developed during this thesis. A first modelling of these spectra is presented in this thesis, and in fine will lead to a much more precise line list for HONO in the 730 - 920 cm-1 region, which will be provided to the scientific community via the HITRAN and GEISA databases and used in the analysis of satellite observations. Regarding HOBr, the aim will be to generate a spectroscopic database in the IR region around 8.6 um, to be used by IASI-NG and FORUM for detection and quantification in the Earth's atmosphere. HOBr plays an important role in atmospheric chemistry and, only exists in laboratory conditions in a mixture characterized by chemical equilibrium: H2O + Br2O = 2(HOBr). The methodology and experimental tools developed during this thesis will be an advantage for implementation of this project, which constitutes the outlook for this work